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Sample records for radiation graft polymerization

  1. Process for radiation grafting hydrogels onto organic polymeric substrates

    DOEpatents

    Ratner, Buddy D.; Hoffman, Allan S.

    1976-01-01

    An improved process for radiation grafting of hydrogels onto organic polymeric substrates is provided comprising the steps of incorporating an effective amount of cupric or ferric ions in an aqueous graft solution consisting of N-vinyl-2 - pyrrolidone or mixture of N-vinyl-2 - pyrrolidone and other monomers, e.g., 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, propylene glycol acrylate, acrylamide, methacrylic acid and methacrylamide, immersing an organic polymeric substrate in the aqueous graft solution and thereafter subjecting the contacted substrate with ionizing radiation.

  2. Sulfonic acid catalysts prepared by radiation-induced graft polymerization

    SciTech Connect

    Mizota, Tomotoshi; Tsuneda, Satoshi; Saito, Kyoichi, Saito

    1994-09-01

    In this study, the authors prepared two variations of graft-type acid catalysts with different adjacent groups by radiation-induced graft polymerization (RIGP), and compared the hydrolytic activity of the resultant acid catalysts for methyl acetate with that of commercially available SO{sub 3}H-type ion-exchange beads with different degrees of cross-linking. 8 refs., 3 figs.

  3. Radiation-induced graft polymerization of amphiphilic monomers with different polymerization characteristics onto hydrophobic polysilane

    NASA Astrophysics Data System (ADS)

    Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro; Sato, Nobuhiro; Matsuyama, Tomochika

    2011-08-01

    The structures of poly(methyl-n-propylsilane) (PMPrS) amphiphilically modified through γ-ray-induced graft polymerization were investigated with 1H NMR measurement. By the use of methyl methacrylate (MMA) or diethyl fumarate (DEF) as monomers for the graft polymerization, grafting yield rose with increasing total absorption dose and monomer concentrations, but decreased with increasing dose rate. This result means that grafting yield of modified PMPrS can be controlled by changing irradiation conditions. However, the number of PMMA or PDEF graft chains per PMPrS chain was estimated to be less than 1.0 by analysis of 1H NMR spectra, and this value was lower than that we had expected. To improve graft density, maleic anhydride (MAH), which is known as a non-homopolymerizable monomer in radical polymerization, was used as a monomer for grafting. As a result, high density grafting (one MAH unit for 4.2 silicon atoms) was attained. It demonstrates that the structure of γ-ray-modified polysilane strongly depends on the polymerization characteristics of grafted monomers.

  4. Antimicrobial fabric adsorbed iodine produced by radiation-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Aoki, Shoji; Fujiwara, Kunio; Sugo, Takanobu; Suzuki, Koichi

    2013-03-01

    Antimicrobial fabric was synthesized by radiation-induced graft polymerization of N-vinyl pyrrolidone onto polyolefine nonwoven fabric and subsequent adsorption of iodine. In response of the huge request for the antimicrobial material applied to face masks for swine flu in 2009, operation procedure of continuous radiation-induced graft polymerization apparatus was improved. The improved grafting production per week increased 3.8 times compared to the production by former operation procedure. Shipped antimicrobial fabric had reached 130,000 m2 from June until December, 2009.

  5. Graft polymerization using radiation-induced peroxides and application to textile dyeing

    NASA Astrophysics Data System (ADS)

    Enomoto, Ichiro; Katsumura, Yosuke; Kudo, Hisaaki; Soeda, Shin

    2011-02-01

    To improve the dyeing affinity of ultra high molecular weight polyethylene (UHMWPE) fiber, surface treatment by radiation-induced graft polymerization was performed. Methyl methacrylate (MMA), acrylic acid (AA) and styrene (St) were used as the monomers. The grafting yields as a function of storage time after irradiation were examined. Although the grafting yield of St after the sulfonation processing was quite low compared with those of MMA and AA, it was successfully dyed to a dark color with a cationic dye. Some acid dyes can dye the grafted fiber with AA. The acid dye is distributed to the amorphous domains of the AA grafted fiber. The dyeing concentration depended on the grafting yield, and the higher the grafting yield the darker the dye color.

  6. The use of radiation-induced graft polymerization for modification of polymer track membranes

    NASA Astrophysics Data System (ADS)

    Shtanko, N. I.; Kabanov, V. Ya.; Apel, P. Yu.; Yoshida, M.

    1999-05-01

    Track membranes (TM) made of poly(ethylene terephtalate) (PET) and polypropylene (PP) films have a number of peculiarities as compared with other ones. They have high mechanical strength at a low thickness, narrow pore size distribution, low content of extractables. However, TM have some disadvantages such as low chemical resistance in alkaline media (PET TM), the low water flow rate due to the hydrophobic nature of their surface. The use of radiation-induced graft polymerization makes it possible to improve the basic characteristics of TM. In this communication our results on the modification of PET and PP TM are presented. The modified membranes were prepared by radiation-induced graft polymerization from the liquid phase. Three methods of grafting were used: (a) the direct method in argon atmosphere; (b) the pre-irradiation of TM in air followed by grafting in argon atmosphere; (c) pre-irradiation in vacuum followed by grafting in vacuum without contacting oxygen. The aim of the work was to investigate some properties of TM modified by grafted poly(methylvinyl pyridine) (PMVP) and poly(N-isopropylacrylamide) (PNIPAAM). It was shown that the modification of TM with hydrophilic polymer results in the growth of the water flow rate. In the past few years many works have been devoted to the synthesis of new polymers - the so-called "intelligent" materials - such as PNIPAAM. However, it is very difficult to make thin membranes of this polymer. Recently, it has been proposed to manufacture composite membranes by grafting stimulus-responsive polymers onto TM. Following this principle, we prepared thermosensitive membranes by the radiation-induced graft polymerization of N-isopropylacrylamide (NIPAAM) onto PET TM. PET TM with the pore size of about 1 μm and pore density of 10 6 cm -2 were first inserted into a solution of NIPAAM containing inhibitor of homopolymerization (CuCl 2) and then exposed to the γ-rays from a 60Co source. The transport properties of the grafted

  7. Radiation Grafting for the Functionalization and Development of Smart Polymeric Materials.

    PubMed

    Pino-Ramos, Víctor H; Ramos-Ballesteros, Alejandro; López-Saucedo, Felipe; López-Barriguete, Jesús E; Varca, Gustavo H C; Bucio, Emilio

    2016-10-01

    Gamma radiation has been shown particularly useful for the functionalization of surfaces with stimuli-responsive polymers. This method involves the formation of active sites (free radicals) onto the polymeric backbone as a result of the high-energy radiation exposition over the polymeric material. Thus, a microenvironment suitable for the reaction among monomer and/or polymer and the active sites is formed and then leading to propagation to form side-chain grafts. The modification of polymers using high-energy irradiation can be performed by the following methods: direct or simultaneous, pre-irradiation oxidative, and pre-irradiation. The most frequently used ones correspond to the pre-irradiation oxidative method as well as the direct one. Radiation-grafting has many advantages over other conventional methods because it does not require the use of catalyst nor additives to initiate the reaction and usually no changes on the mechanical properties with respect to the pristine polymeric matrix are observed. This chapter is focused on the synthesis of smart polymers and coatings obtained by the use of gamma radiation. In addition, the diverse applications of these materials in the biomedical area are also reported, with focus in drug delivery, sutures, and biosensors. PMID:27573505

  8. Grafting of N,N-dimethylaminoethyl methacrylate from PE/PP nonwoven fabric via radiation-induced RAFT polymerization and quaternization of the grafts

    NASA Astrophysics Data System (ADS)

    Madrid, Jordan F.; Barsbay, Murat; Abad, Lucille; Güven, Olgun

    2016-07-01

    Radiation induced grafting method is one of the most promising grafting techniques and it works successfully together with the reversible addition fragmentation chain transfer (RAFT) polymerization, one of the most prominent controlled free-radical polymerization (CRP) methods. This study reports grafting of N,N-dimethylaminoethyl methacrylate (DMAEMA) from the surface of polyethylene/polypropylene nonwoven fabric (PE/PP NWF) by the combination of radiation-induced initiation and the RAFT polymerization technique. Effects of monomer concentration, absorbed dose and solvent choice on the grafting yield have been investigated. The grafted NWF's were characterized by ATR-FTIR, XPS, SEM, EDX and thermal analysis methods. The results indicated that surface properties were completely altered after grafting compared to pristine PE/PP even for those with very low degree of PDMAEMA grafting. Free homopolymers in solution have been analyzed by GPC in order to obtain information about the grafts. The PDMAEMA grafts on the fabric surfaces were later quaternized with dimethyl sulfate to yield positively charged surfaces that were tested for antibacterial properties.

  9. Radiation-induced graft polymerization of maleic acid and maleic anhydride onto ultra-fine powdered styrene butadiene rubber (UFSBR)

    NASA Astrophysics Data System (ADS)

    Peng, Jing; Xia, Haibing; Zhai, Maolin; Li, Jiuqiang; Qiao, Jinliang; Wei, Genshuan

    2007-11-01

    The functionalization of ultra-fine powdered styrene-butadiene rubber (UFSBR) was carried out using gamma radiation-induced graft polymerization of maleic acid (MA) and maleic anhydride (MAH), respectively. It was found that the graft yield of MA onto UFSBR increased rapidly up to the peak and then decreased with increasing MA content. Moreover, the peak shifted to the direction of lower MA content with increasing absorbed dose. Similarly, there was the peak of graft yield with increasing MAH content for grafting of MAH onto UFSBR, whereas the peak of graft yield was achieved at 10 wt% MAH content at different absorbed doses. On the other hand, increasing absorbed dose and decreasing monomer contents are useful to improve the graft efficiency of MA and MAH. At high dose and low monomer content, the graft yield of MAH onto UFSBR is higher than that of MA. FTIR spectra confirmed that both MA and MAH can be grafted successfully onto the UFSBR under gamma irradiation, respectively. Comparing with maleation of rubber by melt grafting, the graft yield of MAH on UFSBR is higher, which can be attributed to the network structure and nanometer size of UFSBR as well as high energy provided by radiation.

  10. Molecular Design, Graft Polymerization and Performance Evaluation of Radiation Curable Flame Retardant Monomers Derived from Phosphorus-Nitrogen Systems

    NASA Astrophysics Data System (ADS)

    Edwards, Brian Tyndall

    The textile industry is constantly seeking new technologies to make its production more efficient, economical and environmentally friendly. An exciting new strategy to impart value-added functional finishes to textiles is the use of radiation, such as ultraviolet (UV) light, to drive the polymerization of monomers onto the surface of the substrates. These grafted polymeric layers provide the fiber or fabric with interesting new properties, such as antimicrobial behavior, water and oil repellency or flame retardancy. With the aid of a photoinitiator, UV curing can take place very rapidly and the process is waterless and uses less energy than traditional textile wet processing. With these thoughts in mind, this research explores the molecular design, synthesis, UV induced graft polymerization and performance evaluation of nine phosphorus-based flame retardant monomers for cellulosic cotton substrates. All monomers in this work were easily prepared using one-pot reactions procedures. With the assistance of Irgacure 819 photoinitiator, seven of the nine monomers were shown to simultaneously graft and polymerize onto the surface of cotton fabrics under UV radiation. JMPRTM Pro 10 software was used to explore the effect of variables, such as monomer concentration, photoinitiator concentration and UV exposure time, on the yield of the grafted polymeric layer. Burn testing of the treated fabrics in the vertical, 45° and horizontal orientations showed that all nine monomers were effective flame retardants that function via the condensed phase mechanism by encouraging the formation of nonflammable char. These burn test results were validated by thermogravimetric analysis, which demonstrated quantitatively that all nine monomers strongly promote the generation of a protective char. Finally, scanning electron microscopy was used to examine the surface morphology of the treated fabrics and visualize the grafted polymeric layer.

  11. Radiation-induced graft polymerization of chitosan onto poly(3-hydroxybutyrate).

    PubMed

    Torres, Maykel González; Muñoz, Susana Vargas; Rosales, Silvia G Solís; Carreón-Castro, Ma del Pilar; Muñoz, Rodrigo Alonso Esparza; González, Roberto Olayo; González, Miriam Rocío Estévez; Talavera, Rogelio Rodríguez

    2015-11-20

    Chitosan is among the most studied biopolymers and offers important advantages, such as biodegradability, biocompatibility and nontoxicity. In this study, this polysaccharide was grafted onto poly(3-hydroxybutyrate) using the simultaneous gamma-irradiation-initiated polymerization method. The polyester was immersed in diverse solvents, which allowed the preparation of graft copolymers with different yields and crystallinities. A successful synthesis and the estimation of the degree of crystallinity were verified by spectroscopic and calorimetric techniques. The most suitable method was found to be the thermoanalytical approach because it displayed a linear relationship between the degree of crystallinity and the increasing degree of grafting. The results also indicated that the lowest degree of grafting was seen for acetic acid (14.27%), while the highest degree corresponded to ethyl acetate (32.11%). The mechanism of grafting was proposed on the basis of the experimental results. PMID:26344305

  12. Desalination by electrodialysis with the ion-exchange membrane prepared by radiation-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Choi, Seong-Ho; Han Jeong, Young; Jeong Ryoo, Jae; Lee, Kwang-Pill

    2001-01-01

    Ion-exchange membranes modified with the triethylamine [-N(CH 2CH 3) 3] and phosphoric acid (-PO 3 H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto the polyolefin nonwavon fabric (PNF) and subsequent chemical modification of poly(GMA) graft chains. The physical and chemical properties of the GMA-grafted PNF and the PNF modified with ion-exchange groups were investigated by SEM, XPS, TGA, and DSC. Furthermore, electrochemical properties such as specific electric resistance, transport number of K +, and desalination were examined. The grafting yield increased with increasing reaction time and reaction temperature. The maximum grafting yield was obtained with 40% (vol.%) monomer concentration in dioxane at 60°C. The content of the cation- and anion-exchange group increased with increasing grafting yield. Electrical resistance of the PNF modified with TEA and -PO 3 H group decreased, while the water uptake (%) increased with increasing ion-exchange group capacities. Transport number of the PNF modified with ion-exchange group were the range of ca. 0.82-0.92. The graft-type ion-exchange membranes prepared by radiation-induced graft copolymerization were successfully applied as separators for electrodialysis.

  13. Graft copolymers of polyurethane with various vinyl monomers via radiation-induced miniemulsion polymerization: Influential factors to grafting efficiency and particle morphology

    NASA Astrophysics Data System (ADS)

    Wang, Hua; Wang, Mozhen; Ge, Xuewu

    2009-02-01

    Graft copolymers of polyurethane (PU) with various vinyl monomers were synthesized through a one-pot but two-step miniemulsion polymerization process. Firstly, the polycondensation of isophorone diisocyanate (IPDI) with hydroxyl-terminated polybutadiene (HTPB) had been performed in aqueous miniemulsion at 40 °C in order to obtain PU dispersions. Consecutively, an in-situ graft copolymerization of the vinyl monomers with the synthesized PU was initiated by γ-ray radiation at room temperature. The grafting efficiency of PU with vinyl monomer ( GPU/monomer) was calculated from 1H NMR spectra and the particle morphology of the final hybrid latex was observed by transmission electron microscopy (TEM). As there was no monomer transferring in miniemulsion system, homogenous hybrid particles would be synthesized provided that the monomer was miscible with PU, such as styrene. With the increase of the polarity of the monomer, the compatibility of PU with monomer decreased. GPU/monomer varied as GPU/styrene(37%)> GPU/butyl acrylate (BA)(21%)> GPU/methyl methacrylate (MMA)(12%). The proportion of homogeneous nucleation would increase as the hydrophilicity of the monomer increased. High temperature would destabilize the miniemulsion so as to result in a less grafting efficiency. Compared to the phase separation during the seeded emulsion polymerization, the miniemulsion polymerization method facilitated the preparation of homogeneous materials owing to its monomer droplet nucleation mechanism.

  14. Preparation and characterization of superhydrophobic organic-inorganic hybrid cotton fabrics via γ-radiation-induced graft polymerization.

    PubMed

    Gao, Qianhong; Hu, Jiangtao; Li, Rong; Pang, Lijuan; Xing, Zhe; Xu, Lu; Wang, Mouhua; Guo, Xiaojing; Wu, Guozhong

    2016-09-20

    A new kind of non-fluorine-based organic-inorganic hybrid superhydrophobic cotton fabric was successfully prepared by simultaneous radiation-induced graft polymerization of γ-methacryloxypropyl trimethoxy silane (MAPS) and subsequent end-capping modification with hexamethyldisilazane (HMDS). The chemical structure and surface topography of the pristine and modified cotton fabrics were investigated in detail by ATR-FTIR, XPS, (29)Si NMR, SEM and TGA to confirm that the graft reaction and end-capping modification had taken place. The above results demonstrated that the grafting polymerization and following end-capping reaction were completed, and a grafting layer was immobilized onto the surface of the cotton fabric. Surface wettability measurement and oil-water separation showed that the modified cotton surface not only exhibited the superhydrophobicity with a water contact angle of 165°, but also afforded a high efficiency of oil-water separation (96%). In particular, this modified cotton fabric retains superhydrophobicity even after 30 laundering cycles or 400 cycles of abrasion. PMID:27261755

  15. Direct pyrolysis mass spectrometry of acrylonitrile-cellulose graft copolymer prepared by radiation-induced graft polymerization in presence of styrene as homopolymer suppressor

    NASA Astrophysics Data System (ADS)

    Badawy, Sayed M.; Dessouki, Ahmad M.; Nizam El-Din, Horia M.

    2001-05-01

    Graft polymerization of acrylonitrile onto cellulosic filter paper competing with the homopolymerization by mutual irradiation technique was studied in the presence of homopolymer suppressors. Addition of FeCl 3 decreased both homopolymerization and graft polymerization, whereas inclusion of a low ratio of styrene monomer with acrylonitrile leads to successful grafting of acrylonitrile with little homopolymer formation. Chemical structure and thermal behavior of the produced graft copolymers were investigated by gradual heating in the solid probe of a mass spectrometer equipped with a GCMS data system. The resulting total ion current (TIC) showed that the degradation of graft copolymers follows two-step pyrolysis. The presence of a low ratio of styrene comonomer increased thermal stability of the prepared acrylonitrile-cellulose graft copolymer. The pyrolysis products have mass spectra characteristic of the copolymer composition; they contain the repeating unit of the oligomers. Total ion current and spectrum subtractions were used to separate and measure spectra of graft copolymers at distinctly different temperatures.

  16. Novel ion-exchange membranes for electrodialysis prepared by radiation-induced graft polymerization

    SciTech Connect

    Tsuneda, Satoshi; Saito, Kyoichi; Misuhara, Hisashi; Sugo, Takanobu

    1995-11-01

    Ion-exchange membranes have been used to concentrate seawater to produce salt as well as to desalinate brackish water to render it potable. Also, the interest in applications of ion-exchange membranes as separators for electrodialytic desalination of bioproducts and separators in hydrogen-oxygen fuel cells has been growing. Novel ion-exchange membranes containing sulfonic acid (SO{sub 3}H) and trimethyl ammonium [N(CH{sub 3}){sub 3}] groups were prepared by a simple method of radiation-induced cografting of sodium styrene sulfonate (SSS) with acrylic acid (AAc) and vinyl benzyl trimethyl ammonium chloride (VBTAC) with 2-hydroxyethyl methacrylate (HEMA), onto a polyethylene film with a thickness of 50 {micro}m. The high density graft chain was introduced throughout the polyethylene film. The maximum cation- and anion-exchange capacities of the resultant membranes were 2.5 and 1.3 mol/kg, receptively. These membranes exhibited an electrical resistance one order lower than commercially available ion-exchange membranes; for example, 12 h cografting provided cation- and anion-exchange membranes whose electrical resistances in a 0.5 M NaCl solution were 0.25 and 0.85 {Omega} cm{sup 2}, respectively. From the evaluation of electrodialytic desalination in a batch mode, using a pair of the graft-type ion-exchange membranes, the time required to achieve 99.5% desalination of the initial 0.5 M NaCl solutions was reduced to 85% comparing with that of the commercial ion-exchange membranes.

  17. Radiation grafting of styrene and acrylonitrile to cellulose and polyethylene

    NASA Astrophysics Data System (ADS)

    Hassanpour, S.

    1999-06-01

    Radiation induced graft polymerization is one of the best methods for obtaining material with new properties. In this work, radiation grafting of styrene, mixture of styrene and acrylonitrile to cellulose and polyethylene in the presence of methanol as a solvent by mutual method is discussed. At a low dose rate, high grafting yields were obtained from the two systems used, due to lesser termination of free radicals with the polymer growing radicals and recombination of primary radicals, resulting in a longer chain length of the grafted copolymer. In the system of styrene and acrylonitrile, comonomer technique was used and the styrene controlled the homopolymer formation during graft polymerization. Water uptake of cellulose decreased by increasing the grafting yields. Grafted cellulose can be molded to some extent and in a high percent of grafting, a new transparent material was obtained. By radiation grafting of styrene-acrylonitrile to low density polyethylene a high degree of crosslinking was observed.

  18. Electron-beam induced RAFT-graft polymerization of poly(acrylic acid) onto PVDF

    NASA Astrophysics Data System (ADS)

    Grasselli, M.; Betz, N.

    2005-07-01

    This paper explores for the first time the post-radiation-induced-graft polymerization on solid substrate using reversible addition-fragmentation transfer (RAFT) mechanism. Radiation-induced graft polymerization onto polymers is a potentially interesting technique to create easily new materials from highly resistant polymers, e.g. surface graft polymerization of acrylic acid (AA) onto poly(vinylidene difluoride) (PVDF) improves its surface properties without losing its excellent mechanical properties. As a consequence of the radical nature of the polymerization processes it is difficult to control molecular weight of grafted chains, and therefore design and standardize the properties of the final product. RAFT polymerization is a suitable method to obtain monodisperse polymers. The ability of the RAFT agents to control the polymer chain length could be an interesting approach to improve the grafted polymers obtained by post-radiation-induced-graft polymerization technique. In this way, graft polymerization of AA onto electron-beam irradiated α-PVDF was performed using trithiocarbonic acid bis(1-phenylethyl) ester as a RAFT agent to control the radical polymerization. We studied several grafting parameters such as solvent, monomer concentration and grafting time in order to achieve a poly(acrylic acid) (PAA) layer onto PVDF surface. Acetic acid was found to be the best solvent for many reasons, as to drive graft polymerization mainly to the polymer surface, complete solubility and stability of all reactants. Hydrolysis of PAA chains was also studied in order to remove the trithiocarbonate functionality from the grafted polymer. A mild chemical condition was achieved in order to have thiol groups that were detected onto the modified PVDF by specific enzymatic reaction.

  19. Radiation graft modification of EPDM rubber

    NASA Astrophysics Data System (ADS)

    Katbab, A. A.; Burford, R. P.; Garnett, J. L.

    N-Vinyl pyrrolidone (NVP), 2-hydroxyethylmethacrylate (HEMA) and acrylamide (AAm) have been grafted to the surface of rubber vulcanizates based on ethylene-propylene-terpolymer (EPDM) using the simultaneous radiation method to alter surface properties such as wettability and therefore biocompatibility. The effect of monomer concentration, solvent and EPDM structural factors on the grafting behavior have been investigated. The inhibitory effect upon homopolymerization of various salts has also been evaluated for the three monomers. NVP and HEMA could be grafted onto EPDM rubber in the presence of aqueous solutions of cupric nitrate at 0.005 M and 1.0 M concentrations respectively. Aqueous solutions of Mohr's salt (ammonium ferrous sulphate) at 0.05 M not only suppressed the homopolymerization of AAm but also increased grafting yield. The percentage grafting also increased with increasing AAm concentration. A mechanism has been proposed to explain the behaviour of these monomers. The inclusion of multifunctional acrylates in additive amounts (1.0 vol%) enhanced the graft degree. Modified samples were able to be efficiently stained, allowing the depth of the graft copolymerization to be determined by light microscopy. Water was found to have an accelerating effect on the polymerization of these monomers, but methanol prevented their polymerization completely. The effect of EPDM structural factors upon degree of grafting was found to vary, depending upon the monomer type.

  20. Acrylic esters in radiation polymerization

    SciTech Connect

    Fomina, N.V.; Khoromskaya, V.A.; Shiryaeva, G.V.

    1988-03-01

    The radiation behavior of (meth)acrylic esters of varying structure was studied. It was shown that in radiation polymerization, in contrast to thermal polymerization, the structure of the ester part can significantly affect the reaction rate and capacity for polymerization in the presence of oxygen. The experimental data are explained from the point of view of consideration of nonvalence effects of the substitutent on the reactivity of the double bond.

  1. Antibacterial cellulose fiber via RAFT surface graft polymerization.

    PubMed

    Roy, Debashish; Knapp, Jeremy S; Guthrie, James T; Perrier, Sébastien

    2008-01-01

    2-(dimethylamino)ethyl methacrylate (DMAEMA) was polymerized from cellulosic filter paper via reversible addition-fragmentation chain transfer (RAFT) polymerization. The tertiary amino groups of the grafted PDMAEMA chains were subsequently quaternized with alkyl bromides of different chain lengths (C8-C16) to provide a large concentration of quaternary ammonium groups on the cellulose surface. The antibacterial activity of the quaternized and nonquaternized PDMAEMA-grafted cellulosic fibers was tested against Escherichia coli. The antibacterial activity was found to depend on the alkyl chain length and on the degree of quaternization, i.e., the amount of quaternary amino groups present in the cellulose graft copolymers. The PDMAEMA-grafted cellulose fiber with the highest degree of quaternization and quaternized with the shortest alkyl chains was found to exhibit particularly high activity against E. coli. PMID:18067264

  2. Supramolecular Polymerization from Polypeptide-Grafted Comb Polymers

    SciTech Connect

    Wang, Jing; Lu, Hua; Kamat, Ranjan K; Pingali, Sai Venkatesh; Urban, Volker S; Cheng, Jianjun; Lin, Yao

    2011-01-01

    The helical and tubular structures self-assembled from proteins have inspired scientists to design synthetic building blocks that can be 'polymerized' into supramolecular polymers through coordinated noncovalent interactions. However, cooperative supramolecular polymerization from large, synthetic macromolecules remains a challenge because of the difficulty of controlling the structure and interactions of macromolecular monomers. Herein we report the synthesis of polypeptide-grafted comb polymers and the use of their tunable secondary interactions in solution to achieve controlled supramolecular polymerization. The resulting tubular supramolecular structures, with external diameters of hundreds of nanometers and lengths of tens of micrometers, are stable and resemble to some extent biological superstructures assembled from proteins. This study shows that highly specific intermolecular interactions between macromolecular monomers can enable the cooperative growth of supramolecular polymers. The general applicability of this strategy was demonstrated by carrying out supramolecular polymerization from gold nanoparticles grafted with the same polypeptides on the surface.

  3. Ethylene vinyl acetate based radiation grafted hydrophilic matrices: Process parameter standardization, grafting kinetics and characterization

    NASA Astrophysics Data System (ADS)

    Chaudhari, C. V.; Mondal, R. K.; Dubey, K. A.; Grover, V.; Panicker, L.; Bhardwaj, Y. K.; Varshney, L.

    2016-08-01

    A transparent, elastomeric, grafted matrix for several potential applications was synthesized by single-step simultaneous radiation grafting of methacrylic acid onto ethylene vinyl acetate (EVA). CuSO4 was found to be the most suitable homo-polymerization inhibitor among different inhibitors tried. The grafting kinetics was found to be a strong function of dose rate (D) and monomer content (M) and an equation relating grafting rate Rg=Kg [M]1.13D0.23 was deduced. Crystallinity of the grafted matrices as assessed from XRD and DSC measurements indicated decrease in crystalline content with increase in grafting yield, suggesting crystalline domain of EVA get disrupted on grafting. Elastic modulus increased linearly with the increase in grafting yield, though elongation at break decreased precipitously from 900% to 30% at even ~9% grafting. Thermo-gravimetric analysis showed three step weight loss of the grafted EVA matrix. The grafting of MAA resulted in increase in surface energy mainly due to enhanced polar component.

  4. Preparation of cassava starch grafted with polystyrene by suspension polymerization.

    PubMed

    Kaewtatip, Kaewta; Tanrattanakul, Varaporn

    2008-09-01

    Cassava starch grafted with polystyrene (PS-g-starch) copolymer was synthesized via free-radical polymerization of styrene by using suspension polymerization technique. Potassium persulfate (PPS) was used as an initiator and water was used as a medium. The graft copolymer was characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, X-ray diffraction and scanning electron microscopy. The sub-micron spherical beads of PS were observed on the surface of starch granules. SEM micrographs showed porous patches of PS adhering on the starch granules after Soxhlet extraction. FTIR spectra also indicated the presence of PS-g-starch copolymer. XRD analysis exhibited insignificant changes in crystalline structure and degree of crystallinity. The effects of starch:styrene weight ratio, amount of PPS, reaction time and reaction temperature on the percentage of grafting - G (%), were investigated. G (%) increased with increasing starch content. Other variables showed their own individual optimal values. The optimum condition yielding 31.47% of G (%) was derived when the component ratio was 1:3 and reaction temperature and time were 50°C and 2h, respectively. Graft copolymerization did not change granular shape and crystallinity of starch. This study demonstrated the capability of polymerization of styrene monomer on the granular starch without emulsifier and the synthesis of graft copolymer without gelatinization of starch. PMID:26048231

  5. Gamma radiation grafted polymers for immobilization of Brucella antigen in diagnostic test studies

    NASA Astrophysics Data System (ADS)

    Docters, E. H.; Smolko, E. E.; Suarez, C. E.

    The radiation grafting process has a wide field of industrial applications, and in the recent years the immobilization of biocomponents in grafted polymeric materials obtained by means of ionizing radiations is a new and important contribution to biotechnology. In the present work, gamma preirradiation grafting method was employed to produce acrylics hydrogels onto polyethylene (PE), polyvinyl chloride (PVC) and polystyrene (PS). Two monomers were used to graft the previously mentioned polymers: methacrylic acid (MAAc) and acrylamide (AAm), and several working conditions were considered as influencing the degree of grafting. All this grafted polymers were used to study the possibility of a subsequent immobilization of Brucella antigen (BAg) in diagnostic test studies (ELISA).

  6. Impact of solvent selection on graft polymerization of acrylamide onto starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The impact on polymer properties [molecular weight, monomer conversion, graft content, graft efficiency and anhydroglucose units between grafts (AGU/graft)] that result from changing the solvent for the graft co-polymerization of acrylamide onto starch from water to dimethylsulfoxide (DMSO) was eval...

  7. Durable Nanolayer Graft Polymerization of Functional Finishes Using Atmospheric Plasma

    NASA Astrophysics Data System (ADS)

    Mazloumpour, Maryam

    Various applications of atmospheric pressure plasma were investigated in conjunction with different chemistries on nonwoven materials including spunbond polyester (PET) and spunbod polypropylene for fuel separation and antimicrobial functionalities. Hydrophobic/Oleophobic properties were conferred on nonwoven polyester (PET) via plasma-induced graft polymerization of different hydrophobic non-C8 perfluorocarbon chemistry including perfluorohexylethylmethacrylate, perfluorohexylethylacrylate, allylpentafluorobenzene, pentafluorostyrene, or 1,3-divinyltetramethyldisiloxane in the vapor form using both in-situ and down-stream plasma configurations. Different nanolayers of the grafted polymer were furnished on nonwovens to generate surfaces with different level of wettabilities for medical applications and water/fuel separation. The effect of various hydrophobic chemistry, different plasma conditions, and plasma device parameters including plasma power and plasma exposure time were studied and the performance was characterized by measuring the contact angle and the wettability rating against liquids with broad range of surface tensions. Vapor deposition of 2-(perfluorohexyl)ethyl methacrylate and pentafluorostyrene on nonwoven PET followed by plasma-induced graft polymerization was investigated for possible use in water/fuel separation. Different nanolayer thicknesses (80-180nm) of the grafted polymer were achieved to generate surfaces with different wettabilities for water/fuel separation of different fuel compositions. The effect of different plasma conditions and device parameters including the flow rate of monomers, power of the device, and time of plasma exposure on the separation of different fuels was studied and characterized by measuring the surface energy of the treated substrates. The surface chemistry and morphology of the treated samples were characterized using XPS, SEM and TOF-SIMS techniques which confirmed the grafting of monomer onto the substrate

  8. Amine functionalization of cellulose surface grafted with glycidyl methacrylate by γ-initiated RAFT polymerization

    NASA Astrophysics Data System (ADS)

    Barsbay, Murat; Güven, Olgun; Kodama, Yasko

    2016-07-01

    This study presents the functionalization of poly(glycidyl methacrylate) (PGMA) grafted cellulose filter paper by a model compound, ethylenediamine (EDA), through the epoxy groups of PGMA. Cellulose based copolymers were prepared via the radiation-induced and RAFT-mediated graft polymerization. The samples were characterized by ATR-FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), elemental analysis, contact angle measurements and scanning electron microscopy (SEM). An efficient modification density of around 1 mmol EDA/mg copolymer was attained within ca. 8 h, indicating that chemical composition of well-defined copolymers may further be tuned by appropriately selecting the reactive agents for use in many emerging fields.

  9. Grafting of thermo-sensitive N-vinylcaprolactam onto silicone rubber through the direct radiation method

    NASA Astrophysics Data System (ADS)

    Valencia-Mora, Ricardo A.; Zavala-Lagunes, Edgar; Bucio, Emilio

    2016-07-01

    The modification of silicone rubber films (SR) was performed by radiation-induced graft polymerization of thermosensitive poly(N-vinylcaprolactam) (PNVCL) using gamma rays from a Co-60 source. The graft polymerization was obtained by a direct radiation method with doses from 5 to 70 kGy, at monomer concentrations between 5% and 70% in toluene. Grafting was confirmed by infrared, differential scanning calorimetry, thermogravimetric analysis, and swelling studies. The lower critical solution temperature (LCST) of the grafted SR was measured by swelling and differential scanning calorimetry.

  10. Preparation of a Proton-Exchange Me mbrane with -SO3H Group Based on Polyethylene and Poly(vinylidene fluoride) Film by Radiation-Induced Graft Polymerization for Proton-Exchange Fuel Cell.

    PubMed

    Kim, Sang-Kyum; Lee, Yong-Sang; Koo, Kee-Kahb; Kim, Sang-Ho; Choi, Seong-Ho

    2015-09-01

    This paper reports the preparation of a proton-exchange membrane (PEM) with sulfonic acid (-SO3H) groups based on polyethylene (PE) films and poly(vinylidene fluoride) (PVdF) films by the radiation-induced graft polymerization (RIGP) of sodium styrene sulfonate (NaSS) in the presence of the polymerizable access agents, such as acrylic acid and pyrollidone in a methanol solution. A PEM with -SO3H based on PE and PVdF films were confirmed by ATR, XPS and contact angle measurements. The water uptake (%), graft yield (%), ion-exchange content (mmol/g), and proton conductivity (S/cm), as well as the current density (mA/cm2), and power density (mW/cm) for PEM with -SO3H groups prepared by RIGP were evaluated. The PEM prepared with the -SO3H groups based on PE and PVdF films can be used as a proton-exchange fuel cell membrane. PMID:26716266

  11. Radiation-hardened polymeric films

    DOEpatents

    Arnold, C. Jr.; Hughes, R.C.; Kepler, R.G.; Kurtz, S.R.

    1984-07-16

    The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10/sup 15/ to 10/sup 21/ molecules of dopant/cm/sup 3/. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

  12. Radiation-hardened polymeric films

    DOEpatents

    Arnold, Jr., Charles; Hughes, Robert C.; Kepler, R. Glen; Kurtz, Steven R.

    1986-01-01

    The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10.sup.15 to 10.sup.21 molecules of dopant/cm.sup.3. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

  13. Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

    SciTech Connect

    Tang, Mingyi; Xu, Xiaoyang; Wu, Tao; Zhang, Sai; Li, Xianxian; Li, Yi

    2014-12-15

    Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.

  14. Polymer brush gradients grafted from plasma-polymerized surfaces.

    PubMed

    Coad, Bryan R; Bilgic, Tugba; Klok, Harm-Anton

    2014-07-22

    A new method for generating a surface density gradient of polymer chains is presented. A substrate-independent polymer deposition technique was used to coat materials with a chemical gradient based on plasma copolymerization of 1,7-octadiene and allylamine. This provided a uniform chemical gradient to which initiators for atom transfer radical polymerization (ATRP) were immobilized. After surface-initiated atom transfer radical polymerization (SI-ATRP), poly(2-hydroxyethyl methacrylate) (PHEMA) chains were grafted from the surface and the measured thickness profiles provided direct evidence for how surface crowding provides an entropic driving force resulting in chain extension away from the surface. Film thicknesses were found to increase with the position along the gradient surface, reflecting the gradual transition from collapsed to more extended surface-tethered polymer chains as the grafting density increased. The method described is novel in that the approach provides covalent linkages from the polymer coating to the substrate and is not limited to a particular surface chemistry of the starting material. PMID:24967529

  15. Biodegradable metal adsorbent synthesized by graft polymerization onto nonwoven cotton fabric

    NASA Astrophysics Data System (ADS)

    Sekine, Ayako; Seko, Noriaki; Tamada, Masao; Suzuki, Yoshio

    2010-01-01

    A fibrous adsorbent for Hg ions was synthesized by radiation-induced emulsion graft polymerization of glycidyl methacrylate (GMA) onto a nonwoven cotton fabric and subsequent chemical modification. The optimal pre-irradiation dose for initiation of the graft polymerization of GMA, which minimized the effects of radiation damage on the mechanical strength of the nonwoven cotton fabric, was found to be 10 kGy. The GMA-grafted nonwoven cotton fabric was subsequently modified with ethylenediamine (EDA) or diethylenetriamine (DETA) to obtain a Hg adsorbent. The resulting amine-type adsorbents were evaluated for batch and continuous adsorption of Hg. In batch adsorption, the distribution coefficients of Hg reached 1.9×10 5 and 1.0×10 5 for EDA- and DETA-type adsorbents, respectively. A column packed with EDA-type adsorbent removed Hg from 1.8 ppm Hg solution at a space velocity of 100 h -1, which corresponds to 16,000 times the volume of the packed adsorbent. The adsorbed Hg on the EDA-type adsorbent could be completely eluted by 1 M HCl solution. A microbial oxidative degradation test revealed that the EDA-type adsorbent is biodegradable.

  16. Radiation effects on polymeric materials

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.

    1988-01-01

    It is important to study changes in properties of polymeres after irradiation with charged particles, with ultraviolet radiation, and with combinations of both. An apparatus for this purpose has been built at the NASA Langley Research Center. It consists of a chamber 9 inches in diameter and 9 inches high with a port for an electron gun, another port for a mass spectrometer, and a quartz window through which an ultraviolet lamp can be focused. The chamber, including the electron gun and the mass spectrometer, can be evacuated to a pressure of 10 to the 8th power torr. A sample placed in the chamber can be irradiated with electrons and ultraviolet radiation separately, sequentially, or simultaneously, while volatile products can be monitored during all irradiations with the mass spectrometer. The apparatus described above has been used to study three different polymer films: lexan; a polycarbonate; P1700, a polysulfone; and mylar, a polyethylene terephthalate. All three polymers had been studied extensively with both electrons and ultraviolet radiation separately, but not simultaneously. Also, volatile products had not been monitored during irradiation for the materials. A high electron dose rate of 530 Mrads/hr was used so that a sufficient concentration of volatile products would be formed to yield a reasonable mass spectrum.

  17. Radiation grafting on natural films

    NASA Astrophysics Data System (ADS)

    Lacroix, M.; Khan, R.; Senna, M.; Sharmin, N.; Salmieri, S.; Safrany, A.

    2014-01-01

    Different methods of polymer grafting using gamma irradiation are reported in the present study for the preparation of newly functionalized biodegradable films, and some important properties related to their mechanical and barrier properties are described. Biodegradable films composed of zein and poly(vinyl alcohol) (PVA) were gamma-irradiated in presence of different ratios of acrylic acid (AAc) monomer for compatibilization purpose. Resulting grafted films (zein/PVA-g-AAc) had their puncture strength (PS=37-40 N mm-1) and puncture deformation (PD=6.5-9.8 mm) improved for 30% and 50% PVA in blend, with 5% AAc under 20 kGy. Methylcellulose (MC)-based films were irradiated in the presence of 2-hydroxyethyl methacrylate (HEMA) or silane, in order to determine the effect of monomer grafting on the mechanical properties of films. It was found that grafted films (MC-g-HEMA and MC-g-silane) using 35% monomer performed higher mechanical properties with PS values of 282-296 N mm-1 and PD of 5.0-5.5 mm under 10 kGy. Compatibilized polycaprolactone (PCL)/chitosan composites were developed via grafting silane in chitosan films. Resulting trilayer grafted composite film (PCL/chitosan-g-silane/PCL) presented superior tensile strength (TS=22 MPa) via possible improvement of interfacial adhesion (PCL/chitosan) when using 25% silane under 10 kGy. Finally, MC-based films containing crystalline nanocellulose (CNC) as a filling agent were prepared and irradiated in presence of trimethylolpropane trimethacrylate (TMPTMA) as a grafted plasticizer. Grafted films (MC-g-TMPTMA) presented superior mechanical properties with a TS of 47.9 MPa and a tensile modulus (TM) of 1792 MPa, possibly due to high yield formation of radicals to promote TMPTMA grafting during irradiation. The addition of CNC led to an additional improvement of the barrier properties, with a significant 25% reduction of water vapor permeability (WVP) of grafted films.

  18. Thermal stability of grafted fibers. [Gamma radiation

    SciTech Connect

    Sundardi, F.; Kadariah; Marlianti, I.

    1983-10-01

    Presented the experimental results on the study of thermal stability of grafted fibers, i.e., polypropylene-, polyester-, and rayon-grafted fibers. These fibers were obtained by radiation grafting processes using hydrophylic monomers such as 1-vinyl 2-pyrolidone, acrylic acid, N-methylol acrylamide, and acrylonitrile. The thermal stability of the fibers was studied using a Shimadzu Thermal Analyzer DT-30. The thermal stability of the fibers, which can be indicated by the value of the activation energy for thermal degradation, was not improved by radiation grafting. The degree of improvement depends on the thermal stability of the monomers used for grafting. The thermal stability of a polypropylene fiber, either a grafted or an ungrafted one, was found to be inferior compared to the polyester of a rayon fiber, which may be due to the lack of C=O and C=C bonds in the polypropylene molecules. The thermal stability of a fiber grafted with acrylonitrile monomer was found to be better than that of an ungrafted one. However, no improvement was detected in the fibers grafted with 1-vinyl 2-pyrrolidone monomer, which may be due to the lower thermal stability of poly(1-vinyl-2-pyrrolidone), compared to the polypropylene or polyester fibers. 17 figures, 3 tables.

  19. Novel biodegradable polymeric flocculant based on polyacrylamide-grafted tamarind kernel polysaccharide.

    PubMed

    Ghosh, Sandipta; Sen, Gautam; Jha, U; Pal, Sagar

    2010-12-01

    Novel biodegradable polymeric flocculants were produced by conventional redox grafting, microwave-initiated and microwave-assisted grafting of acrylamide to tamarind kernel polysaccharide (TKP). The graft copolymers were characterized by viscometry, elemental analysis, molecular weight determination using SLS analysis, and NMR spectroscopy. The flocculation efficiency of the grafting products in kaolin suspension, municipal sewage wastewater and textile industry wastewater was primarily dependent on the length of the grafted polyacrylamide chain. The flocculant obtained by microwave-assisted grafting method was superior to TKP and polyacrylamide-based commercial flocculant (Rishfloc 226 LV) in flocculation tests. PMID:20702087

  20. Light-induced surface graft polymerizations initiated by an anthraquinone dye on cotton fibers.

    PubMed

    Zhuo, Jingyuan; Sun, Gang

    2014-11-01

    Anthraquinone and its derivatives could serve as photo-sensitizers and generate radicals and reactive oxygen species in polymers under exposure of UVA or day light. Such a property was utilized in development of novel light-induced surface radical graft polymerizations on cotton fibers that were dyed with an anthraquinone derivative, 2-ethylanthraquinone. Several functional monomers were directly grafted onto the dyed cotton fibers upon UVA exposure. The chemical and morphological structures and thermal properties of the grafted fibers were confirmed and characterized by Fourier transform infrared spectrometer (FTIR), scanning electron microscope (SEM) and thermal gravimetric analysis (TGA). Reaction conditions including concentrations of the photosensitizer, the amount of monomers, as well as UVA irradiation time could influence grafting efficiencies. More interestingly, the surface graft polymerization did not significantly change the light active functions of the agent, evidenced by the light-active antimicrobial functions of the grafted fibers. PMID:25129730

  1. Encapsulation of silica nanoparticles by redox-initiated graft polymerization from the surface of silica nanoparticles.

    PubMed

    Wang, Huijun; Peng, Mao; Zheng, Jun; Li, Peng

    2008-10-01

    This study describes a facile and versatile method for preparing polymer-encapsulated silica particles by 'grafting from' polymerization initiated by a redox system comprising ceric ion (Ce(4+)) as an oxidant and an organic reductant immobilized on the surface of silica nanoparticles. The silica nanoparticles were firstly modified by 3-aminopropyltriethoxysilane, then reacted with poly(ethylene glycol) acrylate through the Michael addition reaction, so that hydroxyl-terminated poly(ethylene glycol) (PEG) were covalently attached onto the nanoparticle surface and worked as the reductant. Poly(methyl methacrylate) (PMMA), a common hydrophobic polymer, and poly(N-isopropylacrylamide) (PNIPAAm), a thermosensitive polymer, were successfully grafted onto the surface of silica nanoparticles by 'grafting from' polymerization initiated by the redox reaction of Ce(4+) with PEG on the silica surface in acid aqueous solutions. The polymer-encapsulated silica nanoparticles (referred to as silica@PMMA and silica@PNIPAAm, respectively) were characterized by infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. On the contrary, graft polymerization did not occur on bare silica nanoparticles. In addition, during polymerization, sediments were observed for PMMA and for PNIPAAm at a polymerization temperature above its low critical solution temperature (LCST). But the silica@PNIPAAm particles obtained at a polymerization temperature below the LCST can suspend stably in water throughout the polymerization process. PMID:18684468

  2. Radiation-induced graft polymermization of acrylamide onto poly(tetrafluoroethylene/ Hexaflouropropylene/vinylidene fluoride) (TFB) films

    NASA Astrophysics Data System (ADS)

    Dessouki, A. M.; Taher, N. H.; El-Boohy, H. A.

    Radiation-induced graft polymerization of acrylamide (AAm) onto poly(tetrafluoroethylene/ hexafluoropropylene/vinylidene fluoride) (TFB) films has been investigated. The appropriate reaction conditions at which the graft polymerization was carried out successfully were selected. It was observed that the grafting process was enhanced remarkably by using distilled water as diluent. In this grafting system ammonium ferrous sulphate (Mohr's salt) was used as inhibitor to minimize the homopolymerization of AAm and the suitable concentration of such inhibitor was found to be 3.5wt%. The dependence of the grafting rate on the monomer concentration was calculated to be 2.8 order. Some properties of the grafted films such as water uptake, electrical conductivity, mechanical properties and chemical and thermal stability were investigated. An improvement in these properties was observed which makes possible the use of these membranes in some practical applications.

  3. 3D-Printed Biodegradable Polymeric Vascular Grafts.

    PubMed

    Melchiorri, Anthony J; Hibino, Narutoshi; Best, C A; Yi, T; Lee, Y U; Kraynak, C A; Kimerer, Lucas K; Krieger, A; Kim, P; Breuer, Christopher K; Fisher, John P

    2016-02-01

    Congenital heart defect interventions may benefit from the fabrication of patient-specific vascular grafts because of the wide array of anatomies present in children with cardiovascular defects. 3D printing is used to establish a platform for the production of custom vascular grafts, which are biodegradable, mechanically compatible with vascular tissues, and support neotissue formation and growth. PMID:26627057

  4. Surface-initiated graft polymerization on multiwalled carbon nanotubes pretreated by corona discharge at atmospheric pressure.

    PubMed

    Xu, Lihua; Fang, Zhengping; Song, Ping'an; Peng, Mao

    2010-03-01

    Surface-initiated graft polymerization on multi-walled carbon nanotubes pretreated with a corona discharge at atmospheric pressure was explored. The mechanism of the corona-discharge-induced graft polymerization is discussed. The results indicate that MWCNTs were encapsulated by poly(glycidyl methacrylate) (PGMA), demonstrating the formation of PGMA-grafted MWCNTs (PGMA-g-MWCNTs), with a grafting ratio of about 22 wt%. The solubility of PGMA-g-MWCNTs in ethanol was dramatically improved compared to pristine MWCNTs, which could contribute to fabricating high-performance polymer/MWCNTs nanocomposites in the future. Compared with most plasma processes, which operate at low pressures, corona discharge has the merit of working at atmospheric pressure. PMID:20644821

  5. Comparison of surface modifications of poly(ether urethanes) by chemical infusion and graft polymerization

    SciTech Connect

    Wrobleski, D.A.; Cash, D.L.; Hermes, R.E.

    1988-01-01

    Our approach to surface modification uses the chemical infusion process to introduce materials into the outermost layer of the polymeric material, thereby altering the surface without changing the bulk properties of the polymer. The infused materials may slowly diffuse out of the infusion layer if they are volatile or highly mobile. However, if polymeric infusant materials are employed, they may become chain entangled with the host polymer and result in a permanently modified surface. A second approach utilizes photo-initiated graft polymerization of poly(ether urethanes) with an appropriate monomer. We have explored both of these methods by examining the infusion of polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG) into commercially available poly(ether urethanes) and the graft polymerization of N-vinyl pyrrolidone onto poly(ether urethanes). Results are presented here. 7 refs., 1 tab.

  6. Technique of radiation polymerization in fine art conservation: a potentially new method of restoration and preservation. [Uv and electron beams

    SciTech Connect

    Garnett, J.L.; Major, G.

    1982-01-01

    The technique of using radiation polymerization for the restoration and preservation of art treasures is considered. The processes discussed include both radiation grafting and rapid cure procedures, particularly reactions initiated by uv and eb. Representative examples where the technique has already been used are treated including typical applications with paintings, tapestries, leather and archival repair. The structure of the monomers and oligomers used in both grafting and rapid cure systems is outlined. The experimental conditions where grafting may occur during radiation rapid cure processing are discussed. Possible future developments of the technique are outlined. 1 figure, 8 tables.

  7. Radiation grafting of N,N‧-dimethylacrylamide and 2-hydroxyethylmethacrylate onto polypropylene films by one step method

    NASA Astrophysics Data System (ADS)

    Morales-Wiemer, E. A.; Macossay, J.; Bucio, E.

    2013-03-01

    The work presented herein reports on polypropylene films grafted with N,N'-dimethylacrylamide and 2-hydroxyethylmethacrylate. The grafted films were obtained by an oxidative pre-irradiation method in one step using a gamma source of 60Co. The optimal conditions such as reaction time, monomer concentrations and radiation doses were investigated. Characterization of the grafted polymers was carried out through FTIR-ATR, TGA, DSC, and swelling. Grafts onto polymeric films between 10 and 850% were obtained at doses from 20 to 150 kGy and a dose rate of 8.3 kGy/h.

  8. Immobilization of peroxidase on SPEU film via radiation grafting

    NASA Astrophysics Data System (ADS)

    Hongfei, Ha; Guanghui, Wang; Jilan, Wu

    The acrylic acid or acrylamide were grafted via radiation onto segmented polyetherurethane (SPEU) film which is a kind of biocompatible material. Then the Horse radish peroxidase was immobilized on the grafted SPEU film through chemical binding. Some quantitative relationships between the percent graft and the activity, amount of immobilized enzyme were given. The properties and application of obtained biomaterial was studied as well.

  9. The Synthesis of Cellulose Graft Copolymers Using Cu(0)-Mediated Polymerization

    NASA Astrophysics Data System (ADS)

    Donaldson, Jason L.

    Cellulose is the most abundant renewable polymer on the planet and there is great interest in expanding its use beyond its traditional applications. However, its hydrophilicity and insolubility in most common solvent systems are obstacles to its widespread use in advanced materials. One way to counteract this is to attach hydrophobic polymer chains to cellulose: this allows the properties of the copolymer to be tailored by the molecular weight, density, and physical properties of the grafts. Two methods were used here to synthesize the graft copolymers: a 'grafting-from' approach, where synthetic chains were grown outward from bromoester moieties on cellulose (Cell-BiB) via Cu(0)-mediated polymerization; and a 'grafting-to' approach, where fully formed synthetic chains with terminal sulfide functionality were added to cellulose acetate with methacrylate functionality (CA-MAA) via thiol-ene Michael addition. The Cell-BiB was synthesized in the ionic liquid 1-butyl-3-methylimidazolium chloride and had a degree of substitution of 1.13. Polymerization from Cell-BiB proceeded at similar but slightly slower rate than an analogous non-polymeric initiator (EBiB). The average graft density of poly(methyl acrylate) chains was 0.71 chains/ring, with a maximum of 1.0 obtained. The graft density when grafting poly(methyl methacrylate) was only 0.15, and this appeared to be due to the slow initiation of BiB groups. Using EBiB to model the reaction and improve the design should allow this to be overcome. Chain extension experiments demonstrated the living behaviour of the polymer. The CA-MAA was synthesized by esterification with methacrylic acid. Reactions of CA-MAA with thiophenol and dodecanethiol resulted in quantitative addition of the thiol to the alkene. The grafts were synthesized by Cu(0)-mediated polymerization from a bifunctional initiator containing a disulfide bond, followed by reduction to sulfides. The synthetic polymers were successfully grafted to CA-MAA but the

  10. Modification of polymeric substrates using surface-grafted nanoscaffolds

    NASA Astrophysics Data System (ADS)

    Thompson, Kimberlee Fay

    Surface grafting and modification of poly(acrylic acid) (PAA) were performed on nylon 6,6 carpet fibers to achieve permanent stain and soil resistance. PAA was grafted to nylon and modified with 1H, 1H-pentadecafluorooctyl amine (PDFOA) using an amidation agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). The first goal was to optimize acrylamide modification of PAA in solution. Aqueous reactions with taurine, hydroxyethyl amine, and butyl amine progressed ˜100%, while PDFOA reactions in MeOH progressed ˜80%. Reaction products precipitated at 77% butyl or 52% PDFOA acrylamide contents. The second goal was to optimize the PAA grafting process. First, PAA was adsorbed onto nylon 6,6 films. Next, DMTMM initiated grafting of adsorbed PAA. PAA surface coverage was ˜78%, determined by contact angle analysis of the top 0.1--1 nm and x-ray photoelectron spectroscopy (XPS) analysis of the top 3--10 nm. The third goal was to modify PAA grafted nylon films with butyl amine and PDFOA. Randomly methylated beta-cyclodextrin (RAMEB) solubilized PDFOA in water. Contact angle detected ˜100% surface reaction for each amine, while XPS detected ˜77% butyl amine (H2O) and ˜50% for PDFOA (MeOH or H2O pH = 7) reactions. In H2O pH = 12, the PDFOA reaction progressed ˜89%, perhaps due to greater efficiency, access and solubility. The fourth goal was to perform surface depth profiling via angle-resolved XPS analysis (ARXPS). The PAA surface coverage from contact angle and XPS was confirmed. Further, adsorbed PAA was thicker than grafted PAA, supporting the theory that PAA adsorption occurs in thick layers onto nylon followed by DMTMM-activated spreading and grafting of thinner PAA layers across the surface. The PDFOA reaction in McOH produced a highly fluorinated but thin exterior and an unreacted PAA interior. The PDFOA reaction in H 2O pH = 12 produced a completely fluorinated exterior and highly fluorinated interior. Thus surface modification levels

  11. The effects of early postoperative radiation on vascularized bone grafts

    SciTech Connect

    Evans, H.B.; Brown, S.; Hurst, L.N. )

    1991-06-01

    The effects of early postoperative radiation were assessed in free nonvascularized and free vascularized rib grafts in the canine model. The mandibles of one-half of the dogs were exposed to a cobalt 60 radiation dose of 4080 cGy over a 4-week period, starting 2 weeks postoperatively. The patency of vascularized grafts was confirmed with bone scintigraphy. Histological studies, including ultraviolet microscopy with trifluorochrome labeling, and histomorphometric analyses were performed. Osteocytes persist within the cortex of the vascularized nonradiated grafts to a much greater extent than in nonvascularized, nonradiated grafts. Cortical osteocytes do not persist in either vascularized or nonvascularized grafts subjected to radiation. New bone formation is significantly retarded in radiated grafts compared with nonradiated grafts. Periosteum and endosteum remained viable in the radiated vascularized grafts, producing both bone union and increased bone turnover, neither of which were evident to any significant extent in nonvascularized grafts. Bone union was achieved in vascularized and non-vascularized nonradiated bone. In the radiated group of dogs, union was only seen in the vascularized bone grafts.

  12. Radiation grafting of styrene on starch with high efficiency

    NASA Astrophysics Data System (ADS)

    Sheikh, N.; Akhavan, A.; Ataeivarjovi, E.

    2013-04-01

    Wheat starch grafted with polystyrene (PS-g-starch) was synthesized via polymerization grafting of styrene on starch by gamma-ray. The effects of starch/styrene weight ratio, and amount of applied doses (5-40 kGy) on the percentage of grafting, G (%), were investigated. The results showed that G (%) increased with increasing starch content. The optimum condition, starch/styrene weight ratio 1/3 and the applied dose 10 kGy, led to 252.9% of grafting. The obtained graft copolymer was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, and scanning electron microscopy. FTIR spectroscopy as well as the XRD analysis exhibited the changes in chemical and crystalline structure of starch after grafting reaction. TGA demonstrated the changes in thermal stability of PS-g-starch copolymer. SEM micrographs indicated porous patches of PS adhering on the starch.

  13. Membrane surface modification via polymer grafting and interfacial polymerization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Membrane separation is an important technology for separating food ingredients and fractionating high-value substances from food processing by-products. Long-term uses of polymeric membranes in food protein processing are impeded by formation of fouled layers on the membrane surface. Surface modif...

  14. A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

    NASA Astrophysics Data System (ADS)

    Barsbay, Murat; Güven, Olgun

    2009-12-01

    Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.

  15. Preparation and Characterization of Polymeric Surfactants Based on Epoxidized Soybean Oil Grafted Hydroxyethyl Cellulose.

    PubMed

    Huang, Xujuan; Liu, He; Shang, Shibin; Rao, Xiaoping; Song, Jie

    2015-10-21

    Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC) was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC acted as initiators and the polymeric ESO were covalently bonded to the HEC. Hydrolysis of ESO-grafted HEC (ESO-HEC) was performed with sodium hydroxide, and the hydrolyzed ESO-HEC (H-ESO-HEC) products were characterized via Fourier transform infrared (FT-IR) and (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopies, high-temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The results indicated that ring-opening polymerization of ESO occurred with the hydroxyl groups of HEC as initiators. The molecular weights of the H-ESO-HEC products were varied by adjusting the mass ratio of HEC and ESO. Through neutralizing the carboxylic acid of H-ESO-HEC with sodium hydroxide, novel polymeric surfactants (H-ESO-HEC-Na) were obtained, and the effects of polymeric surfactants on the surface tension of water were investigated as a function of concentration of H-ESO-HEC-Na. The H-ESO-HEC-Na was effective at lowering the surface tension of water to 26.33 mN/m, and the critical micelle concentration (CMC) value decreased from 1.053 to 0.157 g/L with increases in molecular weights of the polymeric surfactants. Rheological measurements indicated that the H-ESO-HEC-Na solutions changed from pseudoplastic property to Newtonian with increasing shear rate. PMID:26416659

  16. Integration of lignin and acrylic monomers towards grafted copolymers by free radical polymerization.

    PubMed

    Liu, Xiaohuan; Xu, Yuzhi; Yu, Juan; Li, Shouhai; Wang, Jifu; Wang, Chunpeng; Chu, Fuxiang

    2014-06-01

    Three kinds of acrylic monomers (2,2,3,4,4,4-hexafluorobutyl methacrylate (HFBMA), methyl methacrylate (MMA) and butyl acrylate (BA)) were utilized to modify the lignin (BBL) by "grafting from" free radical polymerization (FRP), respectively. Calcium chloride/hydrogen peroxide (CaCl2/H2O2) was used as initiator. Effects of monomer type and concentration, initiator concentration and polymerization time on grafting from BBL were studied. Grafting of poly (acrylic monomers) onto BBL was verified by the following characterizations and this synthesis method was found to be high efficient and selective for grafting polymerization of BBL. The presence of the BBL moiety in the backbone also resulted in higher glass transition temperature compared with the homopolymer of each monomer, and some modified copolymers also improved its thermal stability. All modifications made BBL more hydrophobic and the static contact angles of these modified copolymers were above 80°. XPS analysis revealed that the surface of these modified BBL copolymers were dominated by acrylate monomer moiety. Additionally, the BBL-g-PBA copolymers can be used as dispersion modifiers in PLA-based materials to enhance UV absorption. PMID:24742785

  17. Enhanced Polymer Grafting from Multiwalled Carbon Nanotubes through Living Anionic Surface-Initiated Polymerization.

    SciTech Connect

    Sakellariou, Georgios; Ji, Haining; Mays, Jimmy; Baskaran, Durairaj

    2008-01-01

    Anionic surface-initiated polymerization of ethylene oxide and styrene has been performed using multiwalled carbon nanotubes (MWNTs) functionalized with anionic initiators. The surface of MWNTs was modified via covalent attachment of precursor anions such as 4-hydroxyethyl benzocyclobutene (BCBEO) and 1-benzocyclobutene-1 -phenylethylene (BCB-PE) through Diels-Alder cycloaddition at 235 C. Surface-functionalized MWNTs-g-(BCB-EO)n and MWNTs-g-(BCB-PE)n with 23 and 54 wt % precursor initiators, respectively, were used for the polymerizations. Alkoxide anion on the surface of MWNTs-g-(BCB-EO)n was generated through reaction with potassium triphenylmethane for the polymerization of ethylene oxide in tetrahydrofuran and phenyl substituted alkyllithium was generated from the surface of MWNTs-g-(BCB-PE)n using sec-butyllithium for the polymerization of styrene in benzene. In both cases, the initiation was found to be very slow because of the heterogeneous reaction medium. However, the MWNTs gradually dispersed in the reaction medium during the polymerization. A pale green color was noticed in the case of ethylene oxide polymerization and the color of initiator as well as the propagating anions was not discernible visually in styrene polymerization. Polymer grafted nanocomposites, MWNTs-g-(BCB-PEO)n and MWNTs-g-(BCB-PS)n containing a very high percentage of hairy polymer with a small fraction of MWNTs (<1 wt %) were obtained. The conversion of ethylene oxide and the weight percent of PEO on the surface of the MWNTs increased with increasing reaction time indicating a controlled polymerization. The polymer-grafted MWNTs were characterized using FTIR, 1H NMR, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy (TEM). Size exclusion chromatography of the polymer grafted MWNTs revealed broad molecular weight distributions (1.3 < Mw/Mn < 1.8) indicating the presence of different sizes of polymer nanocomposites

  18. Biomimetic phosphorylcholine polymer grafting from polydimethylsiloxane surface using photo-induced polymerization.

    PubMed

    Goda, Tatsuro; Konno, Tomohiro; Takai, Madoka; Moro, Toru; Ishihara, Kazuhiko

    2006-10-01

    The biomimetic synthetic phospholipid polymer containing a phosphorylcholine group, 2-methacryloyloxyethyl phosphorylcholine (MPC), has improved the surface property of biomaterials. Both hydrophilic and anti-biofouling surfaces were prepared on polydimethylsiloxane (PDMS) with MPC grafted by surface-initiated photo-induced radical polymerization. Benzophenone was used as the photoinitiator. The quantity of the adsorbed initiator on PDMS was determined by UV absorption and ellipsometry. The poly(MPC)-grafted PDMS surfaces were characterized by XPS, ATR-FTIR and static water contact angle (SCA) measurements. The SCA on PDMS decreased from 115 degrees to 25 degrees after the poly(MPC) grafting. The in vitro single protein adsorption on the poly(MPC)-grafted PDMS decreased 50-75% compared to the unmodified PDMS. The surface friction of the poly(MPC)-grafted PDMS was lower than the unmodified PDMS under wet conditions. The oxygen permeability of the poly(MPC)-grafted PDMS was as high as the unmodified PDMS. The tensile property of PDMS was maintained at about 90% of the ultimate stress and strain after the poly(MPC) grafting. The surface-modified PDMS is expected to be a novel medical elastomer which possesses an excellent surface hydrophilicity, anti-biofouling property, oxygen permeability and tensile property. PMID:16797692

  19. Insolubilisation of biologically active materials with novel radiation graft copolymers

    NASA Astrophysics Data System (ADS)

    Garnett, J. L.; Jankiewicz, S. V.; Levot, R.; Sangster, D. F.

    The use of radiation grafting to immobilise a typical enzyme, trypsin, is reported. The technique involves radiation grafting to a backbone polymer a monomer containing an appropriate functional group to which the enzyme is bonded. In the present work, p-nitrostyrene has been grafted to representative trunk polymers, polypropylene and PVC, the nitro group in the resulting copolymer converted to the isothiocyanato derivative to which trypsin is attached. Of importance to this insolubilisation process, especially for radiation sensitive backbone polymers, is the inclusion of additives which enhance grafting. A new class of additives which increase the grafting yields is reported using as representative backbone polymers, naturally occurring cellulose and synthetic low density polyethylene. The new additives are specific metal salts such as LiClO 4. The reactivity of these salts in grafting enhancement has been compared with that of mineral acid which has previously been used as an additive to increase grafting yields in both preirradiation and simultaneous techniques. A new model for grafting enhancement in the presence of the metal salts as well as acids is proposed whereby increased grafting yields are attributed to increased partitioning of monomer into the graft region in the presence of ionic solutes. The value of these additives in preparing copolymers suitable for general reagent insolubilisation reactions is discussed.

  20. Radiation initiated grafting onto fluoro polymers for membrane preparation

    NASA Astrophysics Data System (ADS)

    El-Assy, N. B.; Dessouki, A. M.

    The radiation initiating grafting of acrylamide (AAm) onto poly(tetrafluoroethylene/ hexafluoropropylene/vinylidene fluoride), TFB, films using the post-radiation grafting technique has been investigated. The factors affecting the grafting process such as radiation dose, dose rate, monomer concentration and temperature on the grafting yield were studied. It was found that the grafting yield is strongly dependent on the dose but independent on the dose rate. The dependence of the grafting rate on monomer concentration was found to be of 1.44 order. The results showed a steady increase of the initial grafting rate with temperature, whereas the final grafting yield passes a maximum around 45°C. The Arrhenius plot reveals two straight lines with different slope intersecting around 35°C. The overall activation energy for this grafting system was calculated and found to be 16.5 and 32.4 kcal/mol above and below 35°C, respectively. This behaviour is presumably correlated to a glass transition of the trunk polymer arising from amorphous material under restraint by crystallites. Some properties of the grafted films such a specific electric resistance, water uptake, mechanical properties and chemical and thermal stability were investigated. An improvement in these properties was observed which makes possible the use of these membranes in some practical applications.

  1. Plasma polymerized thin coating as a protective layer of carbon nanotubes grafted on carbon fibers

    NASA Astrophysics Data System (ADS)

    Einig, A.; Rumeau, P.; Desrousseaux, S.; Magga, Y.; Bai, J. B.

    2013-04-01

    Nanoparticles addition is widely studied to improve properties of carbon fiber reinforced composites. Here, hybrid carbon fiber results from grafting of carbon nanotubes (CNT) by Chemical Vapor Deposition (CVD) on the carbon fiber for mechanical reinforcement and conductive properties. Both tows and woven fabrics made of the hybrid fibers are added to the matrix for composite processing. However handling hybrid fibers may induce unwilling health risk due to eventual CNT release and a protective layer is required. A thin coating layer is deposited homogeneously by low pressure plasma polymerization of an organic monomer without modifying the morphology and the organization of grafted CNTs. The polymeric layer effect on the electrical behavior of hybrid fiber is assessed by conductivity measurements. Its influence on the mechanical properties is also studied regarding the interface adhesion between fiber and matrix. The protective role of layer is demonstrated by means of friction constraints applied to the hybrid fiber.

  2. Surface Grafting via Photo-Induced Copper-Mediated Radical Polymerization at Extremely Low Catalyst Concentrations.

    PubMed

    Laun, Joachim; Vorobii, Mariia; de los Santos Pereira, Andres; Pop-Georgievski, Ognen; Trouillet, Vanessa; Welle, Alexander; Barner-Kowollik, Christopher; Rodriguez-Emmenegger, Cesar; Junkers, Thomas

    2015-09-01

    Surface-initiated photo-induced copper-mediated radical polymerization is employed to graft a wide range of polyacrylate brushes from silicon substrates at extremely low catalyst concentrations. This is the first time that the controlled nature of the reported process is demonstrated via block copolymer formation and re-initiation experiments. In addition to unmatched copper catalyst concentrations in the range of few ppb, film thicknesses up to almost 1 μm are achieved within only 1 h. PMID:26149622

  3. Radiation grafting — state-of-the-art

    NASA Astrophysics Data System (ADS)

    Stannett, Vivian T.

    Radiation grafting is now a process more than 35 years old. In spite of an enermous amount of ingenious research, it has still not led to any large scale commercial exploitation. The same could be said, however, about the various chemical methods of graft copolymerization. Hopeful signs are beginning to appear and some of these possibilities will be discussed. The successful development of new applications of graft copolymers will be the clue to how the whole field develops. Three standard methods of grafting were developed early in the field and are still the main techniques available. These are the mutual (simulataneous), the preirradiation (consecutive), and the peroxide methods. The present status of each and the more modern developments and variations will be discussed in some detail. Although the kinetics of graft copolymerization point towards the lower dose rate gamma radiation sources, there are interesting possibilities with the use of electron beam processing. There is considerable interest, for example, in surface modification with grafting. In this respect, photo-grafting will complete with electron beam processing as it does with radiation curing. Methods of increasing the radiation yields and reducing the formation of homopolymer will also be emphasized. In the past several years, with all methods of grafting including radiation, there has been increased emphasis on applications. This may be regarded as a healthy sign in this fascinating technique.

  4. Graft Polymerization of Acrylic Acid on a Polytetrafluoroethylene Panel by an Inductively Coupled Plasma

    NASA Astrophysics Data System (ADS)

    Lan, Yan; You, Qingliang; Cheng, Cheng; Zhang, Suzhen; Ni, Guohua; Nagatsu, M.; Meng, Yuedong

    2011-02-01

    Surface modification on a polytetrafluoroethylene (PTFE) panel was performed with sequential nitrogen plasma treatments and surface-initiated polymerization. By introducing COO- groups to the surface of the PTFE panel through grafting polymerization of acrylic acid (AA), a transparent poly (acrylic acid) (PAA) membrane was achieved from acrylic acid solution. Grafting polymerization initiating from the active groups was achieved on the PTFE panel surface after the nitrogen plasma treatment. Utilizing the acrylic acid as monomers, with COO- groups as cross link sites to form reticulation structure, a transparent poly (acrylic acid) membrane with arborescent macromolecular structure was formed on the PTFE panel surface. Analysis methods, such as fourier transform infrared spectroscopy (FTIR), microscopy and X-ray photoelectron spectroscopy (XPS), were utilized to characterize the structures of the macromolecule membrane on the PTFE panel surface. A contact angle measurement was performed to characterize the modified PTFE panels. The surface hydrophilicities of modified PTFE panels were significantly enhanced after the plasma treatment. It was shown that the grafting rate is related to the treating time and the power of plasma.

  5. Potassium fulvate as co-interpenetrating agent during graft polymerization of acrylic acid from cellulose.

    PubMed

    Ghazy, Mohamed B M; El-Hai, Farag Abd; Mohamed, Magdy F; Essawy, Hisham A

    2016-10-01

    Grafting polymerization of acrylic acid onto cellulose in presence of potassium fulvate (KF) as a co-interpenetrating agent results enhanced water sorption compared to materials prepared similarly in its absence. The insertion of potassium fulvate (KF) did not affect the grafting process and is thought to proceed in parallel to the graft polymerization via intensive polycondensation reactions of its function groups (-COOH and OH) with COOH of the monomer and OH groups of cellulose. The combination of graft copolymerization and polycondensation reactions is assumed to produce interpenetrating network structure. Fourier transform infrared (FTIR) confirmed successful incorporation within the network structure which is an evidence for formation of interpenetrating network. The obtained structures showed homogeneous uniform surface as revealed by scanning electron microscopy (SEM). The obtained superabsorbent possessed high water absorbency 422 and 48.8g/g in distilled water and saline (0.9wt.% NaCl solution), respectively, and enhanced water retention even at elevated temperatures as revealed by thermogravimetric analysis (TGA). This could be explained by the high content of hydrophilic groups. The new superabsorbents proved to be efficient devices for controlled release of fertilizers which expands their use in agricultural applications. PMID:27370745

  6. Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Li, Xiaomeng; Luan, Shifang; Yang, Huawei; Shi, Hengchong; Zhao, Jie; Jin, Jing; Yin, Jinghua; Stagnaro, Paola

    2012-01-01

    Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.

  7. Polyglycerol dendrimers immobilized on radiation grafted poly-HEMA hydrogels: Surface chemistry characterization and cell adhesion

    NASA Astrophysics Data System (ADS)

    Higa, Olga Z.; Faria, Henrique Antonio Mendonça; de Queiroz, Alvaro A. A.

    2014-05-01

    Radiation induced grafting of poly(2-hydroxyethylmethacrylate) (PHEMA) on low density polyethylene (LDPE) films and subsequent immobilization of poly(glycerol) dendrimer (PGLD) has been performed with the aim to improve cell adhesion and proliferation on the surface of the polymer, in order to enhance their properties for bone tissue engineering scaffolding applications. Radiation grafting of PHEMA onto LDPE was promoted by γ-ray radiation. The covalent immobilization of PGLD on LDPE-g-PHEMA surface was performed by using a dicyclohexyl carbodiimide (DCC)/N,N-dimethylaminopyridine (DMAP) method. The occurrence of grafting polymerization of PHEMA and further immobilization of PGLD was quantitatively confirmed by photoelectron spectroscopy (XPS) and fluorescence, respectively. The LDPE-g-PHEMA surface topography after PGLD coupling was studied by atomic force microscopy (AFM). The hydrophilicity of the LDPE-g-PHEMA film was remarkably improved compared to that of the ungrafted LDPE. The core level XPS ESCA spectrum of PHEMA-grafted LDPE showed two strong peaks at 286.6 eV (from hydroxyl groups and ester groups) and 289.1 eV (from ester groups) due to PHEMA brushes grafted onto LDPE surfaces. The results from the cell adhesion studies show that MCT3-E1 cells tended to spread more slowly on the LDPE-g-PHEMA than on the LDPE-g-PHEMA-i-PGLD.

  8. Entanglements of End Grafted Polymer Brushes in a Polymeric Matrix

    NASA Astrophysics Data System (ADS)

    Grest, Gary S.; Hoy, Robert S.

    2007-03-01

    The entanglement of a polymer brush immersed in a melt of mobile polymer chains is studied by molecular dynamics simulations. A primitive path analysis (PPA) is carried out to identify the brush/brush, brush/melt and melt/melt entanglements as a function of distance from the substrate. The PPA characterizes the microscopic state of conformations of the polymer chain and is ideally suited to identify chain/chain entanglements. We use a new thin-chain PPA technique to eliminate spurious non-entangled inter chain contacts arising from excluded volume. As the grafting density of the brush increases we find that the entanglements of the brush with the melt decrease as the system crosses over from the wet to dry brush regime. Results are compared to brush/brush entanglements in an implicit solvent of varying solvent quality. Sandia is a multiprogram laboratory operated by Sandia Corp., a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  9. Surface modification of microfluidic channels by UV-mediated graft polymerization of non-fouling and ‘smart’ polymers

    NASA Astrophysics Data System (ADS)

    Ebara, Mitsuhiro; Hoffman, John M.; Stayton, Patrick S.; Hoffman, Allan S.

    2007-08-01

    Microfluidic channels prepared from polydimethylsiloxane (PDMS) have been modified by UV-mediated graft polymerization of temperature-responsive polymers (poly[ N-isopropyl acrylamide] or pNIPAAm), temperature- and pH-responsive copolymers (P[NIPAAm-co-acrylic acid (AAc)]), and a non-fouling hydrogel (polyethyleneglycol diacrylate, or PEGDA). This was done by presorbing a photosensitizer (PS) within the PDMS channel surface regions, contacting the different monomer solutions with the PS-containing surface under nitrogen, and irradiating with UV. The pNIPAAm-grafted surface was hydrophilic below its lower critical solution temperature (LCST), resisting non-specific adsorption, while it was hydrophobic above its LCST, now binding pNIPAAm-coated nanoparticles. Combined temperature- and pH-responsive surfaces were also prepared by UV radiation grafting a monomer mixture of pNIPAAm with AAc. The surfaces have been characterized by advancing water contact angle measurements. These smart microfluidic channels should be useful for many applications such as affinity separations and diagnostic assays.

  10. Surface initiated atom transfer radical polymerization grafting of sodium styrene sulfonate from titanium and silicon substrates

    PubMed Central

    Foster, Rami N.; Keefe, Andrew J.; Jiang, Shaoyi; Castner, David G.

    2013-01-01

    This study investigates the grafting of poly-sodium styrene sulfonate (pNaSS) from trichlorosilane/10-undecen-1-yl 2-bromo-2-methylpropionate functionalized Si and Ti substrates by atom transfer radical polymerization (ATRP). The composition, molecular structure, thickness, and topography of the grafted pNaSS films were characterized with x-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), variable angle spectroscopic ellipsometry (VASE), and atomic force microscopy (AFM), respectively. XPS and ToF-SIMS results were consistent with the successful grafting of a thick and uniform pNaSS film on both substrates. VASE and AFM scratch tests showed the films were between 25 and 49 nm thick on Si, and between 13 and 35 nm thick on Ti. AFM determined root-mean-square roughness values were ∼2 nm on both Si and Ti substrates. Therefore, ATRP grafting is capable of producing relatively smooth, thick, and chemically homogeneous pNaSS films on Si and Ti substrates. These films will be used in subsequent studies to test the hypothesis that pNaSS-grafted Ti implants preferentially adsorb certain plasma proteins in an orientation and conformation that modulates the foreign body response and promotes formation of new bone. PMID:24482558

  11. Utilizing advanced polymerization techniques for simplifying polymer grafting from silica colloidal crystal substrates

    NASA Astrophysics Data System (ADS)

    Yerneni, Charu K.

    Polyacrylamide has been well established as a biocompatible material when Polyacrylamide gel electrophoresis (PAGE) came into existence in the 1960s. Under aqueous buffer conditions it becomes non-adsorptive to proteins and due to its molecular level pore forming nature could be used in size based biomolecule separations. Since then considerable research has been done to explore the non-adsorptive nature of polyacrylamide on a platform or substrate. Attempts were made to grow polyacrylamide chains from silica as a substrate which can then be used in various protein separation techniques. Based on an ionic polymerization method which was used for gel casting in PAGE, polymers were grown on silica gel. Though considerable thickness could be achieved, polymerization was not just confined to the surface. Therefore a rigid polymer brush layer could not be achieved. Atom transfer radical polymerization (ATRP) method showed the solution to this problem. Polymer brush layers with acceptable thickness could now be achieved for growing polyacrylamide from silica gel. Yet it still suffered from several disadvantages such as the need of an inert atmosphere for polymerization and limited thickness. Many developments have taken place in the past decade which led to improvements in substrate and polymerization methods. This research used non porous sub-micron silica as the substrate and AGET ATRP (Activator generated electron transfer atom transfer radical polymerization) for surface grafting polyacrylamide. Non porous submicron silica has been shown to be a better stationary phase substrate for protein separations than conventional substrates. AGET ATRP enables polymerization to be performed under ambient conditions and in water based solutions which gives thicknesses much higher than conventional ATRP. Data from various analytical techniques showed that within the experimental range the polymerization is linear and has decent control. This means silica nanoparticles coated with

  12. Kinetics of radiation-induced graft copolymerization of vinyl acetate onto ethylene-co-propylene rubber membranes

    NASA Astrophysics Data System (ADS)

    Yue-E, Fang; Lu Xiao Bing; Wang Shan Zhi; Xia, Zhao; Wang, Fang

    1997-02-01

    The kinetics of radiation-induced graft copolymerization of vinyl acetate onto ethylene-co-propylene rubber (EPR) membrane has been studied in methanol with a radiation source of cobalt-60. The effect of monomer concentration, dose rate, Cu 2+ concentration and temperature on the grafting rate were investigated. The results show that the functional relationship is dg 0/ dt = k[M] 01.95Ḋ[ Cu2+] 0.5. The apparent activation energy and collision frequency factor of the grafting polymerization are 49 kJ mol -1 and 8.9 × 10 8G% kGy -1h -1mol -2.45L 2.45, respectively. The work established the relationship of the initial grafting rate (d g0/d t) with various effect factors: ln(d g0/d t) = 20.61 - 5894(1/ T) + 1.95 ln[ M] 0 + ln D + 0.5 ln[Cu 2+].

  13. Radiation grafting studies of acrylic acid onto cellulose triacetate membranes

    NASA Astrophysics Data System (ADS)

    Mazzei, R. O.; Smolko, E.; Torres, A.; Tadey, D.; Rocco, C.; Gizzi, L.; Strangis, S.

    2002-05-01

    Polymer surface modifications were obtained by the application of radiation treatments, etching and grafting of acrylic acid monomers on different membranes of cellulose triacetate materials. Cellulose triacetate foils from pellet dissolution and commercial cellulose triacetate solid state nuclear track detector membranes were assayed. Irradiation with fission fragments from Cf-252 source to obtain a porous structure, 25 MeV proton beam and Co-60 γ-source to produce peroxides were employed in the experiments. The present work gives the grafting yield of AAc monomer onto CTA membranes as a function of diverse variables including irradiation parameters ( γ-dose, Cf-252 ff irradiation time, proton fluency and electronic energy loss (d E/d x) e), structural parameters (pore diameter and pore density, etching time and etching temperature) and grafting parameters (monomer and Mohr salt concentration, grafting time and grafting temperature).

  14. Radiation polymerization of diethyl fumarate [rapid communication

    NASA Astrophysics Data System (ADS)

    Alkassiri, Haroun

    2005-05-01

    Diethyl fumarate (DEF) has been polymerized by gamma irradiation using doses in the range 50-300 kGy, and in this dose range the polymerization yield increased almost linearly. The polymer has a glass transition temperature of about -20 °C, softening point about 15 °C, and decomposition temperature 300 °C.

  15. Microwave assisted synthesis of polyacrylamide grafted dextrin (Dxt-g-PAM): Development and application of a novel polymeric flocculant.

    PubMed

    Pal, Sagar; Nasim, T; Patra, A; Ghosh, S; Panda, A B

    2010-12-01

    An efficient polymeric flocculant was synthesized by microwave assisted grafting of polyacrylamide to dextrin. By varying the reaction conditions, various grades of graft copolymers were synthesized to obtain the optimized one. Viscometry, elemental analysis, FTIR spectroscopy, (13)C NMR spectroscopy, determination of molecular weight and radius of gyration using SLS analysis, thermal analysis and SEM analysis were employed to confirm that polyacrylamide has been grafted onto the dextrin backbone. The flocculation efficiency of the grafted products in kaolin suspension was dependent on the molecular weight, radius of gyration and length of the grafted polyacrylamide chains. The flocculant obtained by microwave assisted grafting method was superior to dextrin and polyacrylamide-based commercial flocculant (Rishfloc 226 LV) in flocculation tests. PMID:20728467

  16. Preparation of polymer decorated graphene oxide by γ-ray induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Zhang, Bowu; Zhang, Yujie; Peng, Cheng; Yu, Ming; Li, Linfan; Deng, Bo; Hu, Pengfei; Fan, Chunhai; Li, Jingye; Huang, Qing

    2012-02-01

    Herein, we report a facile approach to decorate graphene oxide (GO) sheets with poly(vinyl acetate) (PVAc) by γ-ray irradiation-induced graft polymerization. The content of PVAc in the obtained sample, i.e., PVAc grafted GO (GO-g-PVAc) is calculated by the loss weight in thermogravimetric analysis (TGA) curves. A GO-g-PVAc sample with a degree of grafting (DG) of 28.5% was well dispersed in common organic solvents and the dispersions obtained were extremely stable at room temperature without any aggregation, even after standing for 2 months. The excellent dispersibility and stability of GO-g-PVAc in common organic solvents are readily rationalized in terms of the full coverage of PVAc chains and solvated layer formation on graphene oxide sheets surface, which weakens the interlaminar attraction of GO sheets. This approach presents a facile route for the preparation of dispersible GO and shows great potential in the preparation of graphene-based composites by solution-processes.Herein, we report a facile approach to decorate graphene oxide (GO) sheets with poly(vinyl acetate) (PVAc) by γ-ray irradiation-induced graft polymerization. The content of PVAc in the obtained sample, i.e., PVAc grafted GO (GO-g-PVAc) is calculated by the loss weight in thermogravimetric analysis (TGA) curves. A GO-g-PVAc sample with a degree of grafting (DG) of 28.5% was well dispersed in common organic solvents and the dispersions obtained were extremely stable at room temperature without any aggregation, even after standing for 2 months. The excellent dispersibility and stability of GO-g-PVAc in common organic solvents are readily rationalized in terms of the full coverage of PVAc chains and solvated layer formation on graphene oxide sheets surface, which weakens the interlaminar attraction of GO sheets. This approach presents a facile route for the preparation of dispersible GO and shows great potential in the preparation of graphene-based composites by solution-processes. Electronic

  17. Plasma graft-polymerization for synthesis of highly stable hydroxide exchange membrane

    NASA Astrophysics Data System (ADS)

    Hu, Jue; Zhang, Chengxu; Jiang, Lin; Fang, Shidong; Zhang, Xiaodong; Wang, Xiangke; Meng, Yuedong

    2014-02-01

    A novel plasma graft-polymerization approach is adopted to prepare hydroxide exchange membranes (HEMs) using cardo polyetherketone powders (PEK-C) and vinylbenzyl chloride. The benzylic chloromethyl groups can be successfully introduced into the PEK-C polymer matrix via plasma graft-polymerization. This approach enables a well preservation in the structure of functional groups and formation of a highly cross-linked structure in the membrane, leading to an improvement on the stability and performance of HEMs. The chemical stabilities, including alkaline and oxidative stability, are evaluated under severe conditions by measuring hydroxide conductivity and weight changes during aging. The obtained PGP-NOH membrane retains 86% of the initial hydroxide conductivity in 6 mol L-1 KOH solution at 60 °C for 120 h, and 94% of the initial weight in 3 wt% H2O2 solution at 60 °C for 262 h. The PGP-NOH membrane also possesses excellent thermal stability (safely used below 120 °C), alcohol resistance (ethanol permeability of 6.6 × 10-11 m2 s-1 and diffusion coefficient of 3.7 × 10-13 m2 s-1), and an acceptable hydroxide conductivity (8.3 mS cm-1 at 20 °C in deionized water), suggesting a good candidate of PGP-NOH membrane for HEMFC applications.

  18. Study of plasma-induced graft polymerization of stearyl methacrylate on cotton fabric substrates

    NASA Astrophysics Data System (ADS)

    Li, Yongqiang; Zhang, Yan; Zou, Chao; Shao, Jianzhong

    2015-12-01

    A simple and facile method to prepare the cotton fabric with hydrophobicity was described in the present work. In the one-step process, the cotton fabric pre-impregnated with the monomer solution of stearyl methacrylate (SMA) was placed in the plasma chamber and followed by glow discharge of the Helium low temperature plasma. The cotton fabrics before and after the plasma treatment were characterized by field emission scanning electron microscopy (FESEM), infrared spectroscopic analysis (FTIR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), respectively. The wettability of the cotton fabrics was evaluated by contact angle measurement. Fabric Hand Values and mechanical properties were also measured in the experiment. The results showed that polymer films could be coated on the cotton fibers through the plasma induced grafting polymerization of SMA. The modified cotton fabrics exhibited an extraordinary hydrophobicity with a contact angle of 149° for a 5 μL water droplet and excellent thermal stability. The relative hand value and mechanical breaking strength of the cotton fabrics declined slightly after graft polymerization of SMA by the plasma.

  19. PEG Molecular Net-Cloth Grafted on Polymeric Substrates and Its Bio-Merits

    NASA Astrophysics Data System (ADS)

    Zhao, Changwen; Lin, Zhifeng; Yin, Huabing; Ma, Yuhong; Xu, Fujian; Yang, Wantai

    2014-05-01

    Polymer brushes and hydrogels are sensitive to the environment, which can cause uncontrolled variations on their performance. Herein, for the first time, we report a non-swelling ``PEG molecular net-cloth'' on a solid surface, fabricated using a novel ``visible light induced surface controlled graft cross-linking polymerization'' (VSCGCP) technique. Via this method, we show that 1) the 3D-network structure of the net-cloth can be precisely modulated and its thickness controlled; 2) the PEG net-cloth has excellent resistance to non-specific protein adsorption and cell adhesion; 3) the mild polymerization conditions (i.e. visible light and room temperature) provided an ideal tool for in situ encapsulation of delicate biomolecules such as enzymes; 4) the successive grafting of reactive three-dimensional patterns on the PEG net-cloth enables the creation of protein microarrays with high signal to noise ratio. Importantly, this strategy is applicable to any C-H containing surface, and can be easily tailored for a broad range of applications.

  20. A mild strategy to encapsulate enzyme into hydrogel layer grafted on polymeric substrate.

    PubMed

    Zhu, Xing; Ma, Yuhong; Zhao, Changwen; Lin, Zhifeng; Zhang, Lihua; Chen, Ruichao; Yang, Wantai

    2014-12-23

    Although the hydrogel network has been widely investigated as a carrier for enzyme immobilization, to in situ encapsulate enzymes into a hydrogel network in an efficient, practical, and active way is still one of the great challenges in the field of biochemical engineering. Here, we report a new protocol to address this issue by encapsulating enzyme into poly(ethylene glycol) (PEG) hydrogel network grafted on polymeric substrates. In our strategy, isopropyl thioxanthone semipinacol (ITXSP) dormant groups were first planted onto the surface of a plastic matrix with low density polyethylene (LDPE) film as a model by a UV-induced abstracting hydrogen-coupling reaction. As a proof of concept, lipase, which could catalyze esterification of glucose with palmitic acid, then was in situ net-immobilized into a PEG-based hydrogel network layer through a visible light-induced surface controlled/living graft cross-linking polymerization. This strategy demonstrates the following novel significant merits: (1) in comparison with the UV irradiation or high temperature, the visible light and room temperature used provide a friendly condition to maintain activity of enzyme during immobilization; (2) the uniqueness of controlled/living cross-linking polymerization not only makes it easy to form a uniform PEG hydrogel network, which is a benefit to avoid the leakage of net-immobilizing enzyme, but also to tune the net-thickness or capacity to accommodate enzyme; and (3) as compared to systems of nanoparticles and porous matrixes, the flexible/robust end-products of the surface net-immobilizing enzyme with polymer film are more suitable to be applied in a bioreactor due to their features of easier separation and reuse. We confirmed that this catalytic film could retain almost all of its initial activity after seven batches of 24 h esterifications. The proposed strategy provides an extremely simple, effective, and flexible method for enzyme immobilization. PMID:25489918

  1. Strategies and Techniques to Enhance the In Situ Endothelialization of Small-Diameter Biodegradable Polymeric Vascular Grafts

    PubMed Central

    Hibino, Narutoshi; Fisher, John P.

    2013-01-01

    Due to the lack of success in small-diameter (<6 mm) prosthetic vascular grafts, a variety of strategies have evolved utilizing a tissue-engineering approach. Much of this work has focused on enhancing the endothelialization of these grafts. A healthy, confluent endothelial layer provides dynamic control over homeo-stasis, influencing and preventing thrombosis and smooth muscle cell proliferation that can lead to intimal hyperplasia. Strategies to improve endothelialization of biodegradable polymeric grafts have encompassed both chemical and physical modifications to graft surfaces, many focusing on the recruitment of endothelial and endothelial progenitor cells. This review aims to provide a compilation of current and developing strategies that utilize in situ endothelialization to improve vascular graft outcomes, providing a context for the future directions of vascular tissue-engineering strategies that do not require preprocedural cell seeding. PMID:23252992

  2. Fabrication and Short-Term in Vivo Performance of a Natural Elastic Lamina-Polymeric Hybrid Vascular Graft.

    PubMed

    McCarthy, Connor W; Ahrens, Danielle C; Joda, David; Curtis, Tyler E; Bowen, Patrick K; Guillory, Roger J; Liu, Shu Q; Zhao, Feng; Frost, Megan C; Goldman, Jeremy

    2015-08-01

    Although significant advances have been made in the development of artificial vascular grafts, small-diameter grafts still suffer from excessive platelet activation, thrombus formation, smooth muscle cell intimal hyperplasia, and high occurrences of restenosis. Recent discoveries demonstrating the excellent blood-contacting properties of the natural elastic lamina have raised the possibility that an acellular elastic lamina could effectively serve as a patent blood-contacting surface in engineered vascular grafts. However, the elastic lamina alone lacks the requisite mechanical properties to function as a viable vascular graft. Here, we have screened a wide range of biodegradable and biostable medical-grade polymers for their ability to adhere to the outer surface of the elastic lamina and allow cellular repopulation following engraftment in the rat abdominal aorta. We demonstrate a novel method for the fabrication of elastic lamina-polymeric hybrid small-diameter vascular grafts and identify poly(ether urethane) (PEU 1074A) as ideal for this purpose. In vivo results demonstrate graft patency over 21 days, with low thrombus formation, mild inflammation, and the general absence of smooth muscle cell hyperplasia on the graft's luminal surface. The results provide a new direction for developing small-diameter vascular grafts that are mass-producible, shelf-stable, and universally compatible due to a lack of immune response and inhibit the in-graft restenosis response that is common to nonautologous materials. PMID:26204095

  3. Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

    PubMed

    Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

    2016-04-01

    Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1)H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. PMID:26847467

  4. Diversity-Oriented Polymerization: One-Shot Synthesis of Library of Graft and Dendronized Polymers by Cu-Catalyzed Multicomponent Polymerization.

    PubMed

    Kim, Hyunseok; Bang, Ki-Taek; Choi, Inho; Lee, Jin-Kyung; Choi, Tae-Lim

    2016-07-13

    Graft and dendronized polymers have attracted much attention in the polymer community, and there have been significant efforts to develop better synthetic methods. Herein, we report the highly efficient synthesis of graft and dendronized polymers by using Cu-catalyzed multicomponent polymerization (MCP). Based on diversity-oriented synthesis, we prepared a library of various graft and dendronized polymers from combinations of three types of monomers (mono-functionalized alkynes, bis-sulfonyl azides, and diamines/diols) that are bench stable and readily accessible. After reaction optimization, 54 samples of high-molecular-weight graft and dendronized polymers were prepared, the MCP method allowing simultaneous manipulation of the structures of both the main chains and the side chains. Moreover, because of the severe steric hindrance of the side chains, these polymers adopted extended conformations, as shown by the large shape parameter in solution. Also, the extended morphology of the single polymer chains was directly visualized by atomic force microscopy and transmission electron microscopy in the solid state. Most importantly, this diversity-oriented polymerization became possible because of highly step-economical and efficient one-step MCP, paving the way toward the easily tunable synthesis of graft and dendronized polymers. PMID:27355448

  5. Evaluation of microwave assisted grafted sago starch as controlled release polymeric carrier.

    PubMed

    Singh, Akhilesh Vikram; Nath, Lila Kanta

    2013-09-01

    In the present investigation an attempt has been made to develop a new co-polymeric material for controlled release tablet formulations. The acrylamide grafting was successfully performed on the backbone of sago starch. The modified starch was tested for acute toxicity and drug-excipient compatibility study. The grafted material was used in making of controlled release tablets of lamivudine. The formulations were evaluated for physical characteristics such as hardness, friability, %drug content and weight variations. The in vitro release study showed that the optimized formulation exhibited highest correlation (R) value in case of Higuchi model and the release mechanism of the optimized formulation predominantly exhibited combination of diffusion and erosion process. There was a significant difference in the pharmacokinetic parameters (T(max), C(max), AUC, V(d), T(1/2) and MDT) of the optimized formulation as compared to the marketed conventional tablet Lamivir(®) was observed. The pharmacokinetics parameters were showed controlled pattern and better bioavailability. The optimized formulation exhibited good stability and release profile at the accelerated stability conditions. PMID:23707750

  6. Ring-opening graft polymerization of propylene carbonate onto xylan in an ionic liquid.

    PubMed

    Zhang, Xueqin; Chen, Mingjie; Liu, Chuanfu; Zhang, Aiping; Sun, Runcang

    2015-01-01

    The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young's modulus of the films decreased, while the elongation at break increased. PMID:25853319

  7. Bacterial attachment to RO membranes surface-modified by concentration-polarization-enhanced graft polymerization.

    PubMed

    Bernstein, Roy; Belfer, Sofia; Freger, Viatcheslav

    2011-07-15

    Concentration polarization-enhanced radical graft polymerization, a facile surface modification technique, was examined as an approach to reduce bacterial deposition onto RO membranes and thus contribute to mitigation of biofouling. For this purpose an RO membrane ESPA-1 was surface-grafted with a zwitterionic and negatively and positively charged monomers. The low monomer concentrations and low degrees of grafting employed in modifications moderately reduced flux (by 20-40%) and did not affect salt rejection, yet produced substantial changes in surface chemistry, charge and hydrophilicity. The propensity to bacterial attachment of original and modified membranes was assessed using bacterial deposition tests carried out in a parallel plate flow setup using a fluorescent strain of Pseudomonas fluorescens. Compared to unmodified ESPA-1 the deposition (mass transfer) coefficient was significantly increased for modification with the positively charged monomer. On the other hand, a substantial reduction in bacterial deposition rates was observed for membranes modified with zwitterionic monomer and, still more, with very hydrophilic negatively charged monomers. This trend is well explained by the effects of surface charge (as measured by ζ-potential) and hydrophilicity (contact angle). It also well correlated with force distance measurements by AFM using surrogate spherical probes with a negative surface charge mimicking the bacterial surface. The positively charged surface showed a strong hysteresis with a large adhesion force, which was weaker for unmodified ESPA-1 and still weaker for zwitterionic surface, while negatively charged surface showed a long-range repulsion and negligible hysteresis. These results demonstrate the potential of using the proposed surface- modification approach for varying surface characteristics, charge and hydrophilicity, and thus minimizing bacterial deposition and potentially reducing propensity biofouling. PMID:21682251

  8. Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via UV-induced graft polymerization of N-vinyl pyrrolidone.

    PubMed

    Luan, Shifang; Zhao, Jie; Yang, Huawei; Shi, Hengchong; Jin, Jing; Li, Xiaomeng; Liu, Jingchuan; Wang, Jianwei; Yin, Jinghua; Stagnaro, Paola

    2012-05-01

    Poly(N-vinyl pyrrolidone) (PNVP) was covalently grafted onto the surface of biomedical poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) elastomer via a technique of UV-induced graft polymerization combined with plasma pre-treatment. The surface graft polymerization of N-vinyl pyrrolidone (NVP) was confirmed by ATR-FTIR and XPS. Effect of the parameters of graft polymerization, i.e., the initiator concentration, the UV irradiation time and the monomer concentration on the grafting density was investigated. The morphology and the wettability of the PNVP-modified surfaces were characterized by AFM and DSA, respectively. Protein adsorption and platelet adhesion were obviously suppressed after PNVP was grafted onto the SEBS substrates. PMID:22264686

  9. Effect of hydroxyapatite whisker surface graft polymerization on water sorption, solubility and bioactivity of the dental resin composite.

    PubMed

    Liu, Fengwei; Jiang, Xiaoze; Bao, Shuang; Wang, Ruili; Sun, Bin; Zhu, Meifang

    2015-08-01

    The aim of this study was to investigate the effect of poly bisphenol A glycidyl methacrylate (poly(Bis-GMA)) grafted hydroxyapatite whisker (PGHW) on water sorption, solubility and bioactivity of the dental resin composite. PGHW with different graft ratios was synthesized, by controlling grafting time, and filled into a dental resin matrix respectively. Fracture surface of the resin composites showed that PGHW-matrix interfacial compatibility and bonding were enhanced, and lower amounts of poly(Bis-GMA) on PGHW-1h (graft ratio: 8.5 wt.%) could facilitate the dispersion of PGHW-1 h in the composite. The PGHW-1h filled resin composite absorbed the lowest amount of water (27.16 μg/mm(3), 7 d), whereas the untreated hydroxyapatite whisker (HW) filled resin composite absorbed the highest. PGHW with higher graft ratios induced the decrease of the monomer conversion in the resulting composite, therefore, the PGHW-18 h (graft ratio: 32.8 wt.%) filled resin composite had the highest solubility. In vitro bioactivity of the studied resin composites in simulated body fluid (SBF) showed that a dense and continuous apatite layer was formed on the surface of the resin composite, and the surface graft polymerization on the whisker did not significantly affect the apatite forming ability of the resin composite. It was revealed that graft polymerization of an appropriate amount of Bis-GMA onto HW could be an effective method to improve the interfacial properties and stability in water of the dental resin composite without compromising the bioactivity. PMID:26042702

  10. In-situ graft-polymerization preparation of cation-exchange supermacroporous cryogel with sulfo groups in glass columns.

    PubMed

    Yao, Kejian; Yun, Junxian; Shen, Shaochuan; Chen, Fang

    2007-07-20

    Graft polymerization of monomer chains with expected functional groups onto the matrix pore surfaces by initiator is an effective approach for introducing ion-exchange groups to cryogel matrix to get anion- or cation-exchange supermacroporous cryogels. In this work, a novel cation-exchange cryogel with sulfo binding groups was prepared by grafting of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) onto polyacrylamide-based cryogels in glass columns. The grafting polymerization was achieved in an in-situ manner which was performed by pumping the initiator and the reactive solution of graft monomer with sulfo binding groups directly through a cryogel bed pre-produced in a glass column under frozen condition. The axial liquid dispersion characteristics within the monolithic cryogel beds before and after the in-situ polymerization were compared by measuring residence time distributions (RTDs) at various liquid flow rates using tracer pulse-response method. Microstructure morphology of pores within cryogels was analyzed by scanning electron microscopy (SEM). Chromatography of lysozyme was carried out to reveal the protein breakthrough and elution characteristics in the obtained cryogel beds. PMID:17517417

  11. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    NASA Astrophysics Data System (ADS)

    Wang, Jingjing; Wei, Jun

    2016-09-01

    Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  12. Polymeric nanocomposite proton exchange membranes prepared by radiation-induced polymerization for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Young-Seok; Seo, Kwang-Seok; Choi, Seong-Ho

    2016-01-01

    The vinyl group-modified montmorillonite clay (F-MMT), vinyl group-modified graphene oxide (F-GO), and vinyl group-modified multi-walled carbon nanotube (F-MWNT) were first prepared by ion exchange reaction of 1-[(4-ethylphenyl)methyl]-3-butyl-imidazolium chloride in order to use the materials for protection against methanol cross-over in direct methanol fuel cell (DMFC) membrane. Then polymeric nanocomposite membranes with F-MMT, F-GO, and F-MWNT were prepared by the solvent casting method after radiation-induced polymerization of vinyl monomers in water-methanol mixture solvents. The proton conductivity, water uptake, ion-exchange capacity, methanol permeability, and DMFC performance of the polymeric nanocomposite membranes with F-MMT, F-GO, and F-MWNT were evaluated.

  13. Space radiation resistant transparent polymeric materials

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.

    1977-01-01

    A literature search in the field of ultraviolet and charged particle irradiation of polymers was utilized in an experimental program aimed at the development of radiation stable materials for space applications. The rationale utilized for material selection and the synthesis, characterization and testing performed on several selected materials is described. Among the materials tested for ultraviolet stability in vacuum were: polyethyleneoxide, polyvinylnaphthalene, and the amino resin synthesized by the condensation of o-hydroxybenzoguanamine with formaldehyde. Particularly interesting was the radiation behavior of poly(ethyleneoxide), irradiation did not cause degradation of optical properties but rather an improvement in transparency as indicated by a decrease in solar absorptance with increasing exposure time.

  14. Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

    DOE PAGESBeta

    Wang, Wenwen; Wang, Weiyu; Li, Hui; Lu, Xinyi; Chen, Jihua; Kang, Nam-goo; Zhang, Qiuyu; Mays, Jimmy

    2015-01-14

    In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 105 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

  15. Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

    SciTech Connect

    Wang, Wenwen; Wang, Weiyu; Li, Hui; Lu, Xinyi; Chen, Jihua; Kang, Nam-goo; Zhang, Qiuyu; Mays, Jimmy

    2015-01-14

    In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermal analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 105 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.

  16. Preparation of poly(methyl methacrylate) grafted titanate nanotubes by in situ atom transfer radical polymerization.

    PubMed

    Gao, Yuan; Gao, Xueping; Zhou, Yongfeng; Yan, Deyue

    2008-12-10

    This paper reports the successful preparation of core-shell hybrid nanocomposites by a 'grafting from' approach based on in situ atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) from titanate nanotubes (TNTs). Transmission electron microscope (TEM) images of the products provide direct evidence for the formation of a core-shell structure, possessing a hard core of TNTs and a soft shell of poly-MMA (PMMA). Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance ((1)H NMR), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) were used to determine the chemical structure, morphology, and the grafted PMMA quantities of the resulting products. The grafted PMMA content was well controlled and increased with increasing monomer/initiator ratio. Further copolymerization of hydroxyethyl methacrylate (HEMA) with PMMA-coated TNTs as initiators was realized, illustrating the 'living' characteristics of the ATRP method used in this paper. PMID:21730679

  17. BenzoDODA grafted polymeric resin-Plutonium selective solid sorbent.

    PubMed

    Ruhela, R; Panja, S; Singh, A K; Dhami, P S; Gandhi, P M

    2016-11-15

    A new ligand grafted polymeric resin (BenzoDODA SDVB) was synthesized by covalently attaching plutonium selective ligand (BenzoDODA) on to styrene divinyl benzene (SDVB) polymer matrix. BenzoDODA SDVB resin was evaluated for separation and recovery of plutonium(IV) from nitric acid medium. Sorption of Pu(IV) was found to decrease with the increase in nitric acid concentration, with very small sorption above 7.0M HNO3. Sorption kinetics was fast enough to achieve the equilibrium within 60min of contact where the kinetic data fitted well to pseudo-second-order model. Sorption isotherm data fitted well to Langmuir model suggesting chemical interaction between the BenzoDODA moiety and plutonium(IV) ions. Sorption studies with some of representative radionuclides of high level waste showed that BenzoDODA SDVB is selective and therefore could be a promising solid sorbent for separation and recovery of plutonium. Further, the theoretical calculations done on BenzoDODA SDVB resin suggested Pu(NO3)4·BenzoDODA (1:1) sorbed complex conformed to generally observed square antiprism geometry of the plutonium complexes, with contributions from oxygen atoms of four nitrate ions as well as from four oxygen atoms present in BenzoDODA (two phenolic ether oxygen atoms and two carbonyl oxygen atoms of amidic moiety). PMID:27420390

  18. Hydroxyapatite surface modified by L-lactic acid and its subsequent grafting polymerization of L-lactide.

    PubMed

    Qiu, Xueyu; Hong, Zhongkui; Hu, Junli; Chen, Li; Chen, Xuesi; Jing, Xiabin

    2005-01-01

    A new method of surface modification of hydroxyapatite nanoparticles (n-HA) by surface grafting reaction of l-lactic acid and ring-opening polymerization of l-lactide (LLA) was developed. Two modified HA nanoparticles were obtained: HA modified by l-lactic acid (l-HA) and HA grafting with poly(l-lactide) (PLLA; p-HA). The modified surface of n-HA was attested by Fourier transformation infrared, (31)P MAS NMR, and thermal gravimetric analysis. The results showed that l-lactic acid could be easily grafted onto the n-HA surface by forming a Ca carboxylate bond and initiated by the hydroxyl group of the grafted l-lactic acid and LLA could be graft-polymerized onto the n-HA surface in the presence of stannous octanoate. The highest grafting amounts of l-lactic acid and PLLA were about 33 and 22 wt %, respectively. The modified HA/PLLA composites showed good mechanical properties and uniform microstructure. The tensile strength and modulus of the p-HA/PLLA composite containing 15 wt % of p-HA were 67 MPa and 2.1 GPa, respectively, while those of the n-HA/PLLA composites were 45 MPa and 1.7 GPa, respectively. The elongation at the break of the l-HA/PLLA composite containing 15 wt % l-HA could reach 44%, in comparison with 6.5% of the n-HA/PLLA composites containing 15 wt % n-HA. PMID:15877333

  19. Radiation grafted adsorbents for newly emerging environmental applications

    NASA Astrophysics Data System (ADS)

    Mahmoud Nasef, Mohamed; Ting, T. M.; Abbasi, Ali; Layeghi-moghaddam, Alireza; Sara Alinezhad, S.; Hashim, Kamaruddin

    2016-01-01

    Radiation induced grafting (RIG) is acquired to prepare a number of adsorbents for newly emerging environmental applications using a single route involving RIG of glycidymethacrylate (GMA) onto polyethylene-polypropylene (PE-PP) non-woven fabric. The grafted fabric was subjected to one of three functionalization reactions to impart desired ionic characters. This included treatment with (1) N-dimethyl-D-glucamine, (2) triethylamine and (3) triethylamine and alkalisation with KOH. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) were used to study the changes in chemical and physical structures of the obtained fibrous adsorbents. The potential applications of the three adsorbents for removal of boron from solutions, capturing CO2 from CO2/N2 mixtures and catalysing transesterification of triacetin/methanol to methyl acetate (biodiesel) were explored. The obtained fibrous adsorbents provide potential alternatives to granular resins for the investigated applications and require further development.

  20. Modification of polyetherurethane for biomedical application by radiation-induced grafting. I. Grafting procedure, determination of mechanical properties, and chemical modification of grafted films

    SciTech Connect

    Jansen, B.; Ellinghorst, G.

    1985-11-01

    Radiation grafting of monomers onto suitable trunk polymers is a useful tool for tailoring new polymers for special purposes. This technique has been used in the past for the development of biocompatible materials, e.g., by grafting hydrogels onto mechanically stable polymers. In this first part of our work, the radiation grafting of hydrophilic or reactive monomers onto a polyetherurethane film using the pre-swelling technique is described. Following this technique the trunk polymer was swollen in the monomer before irradiation. As monomers 2-hydroxyethyl methacrylate (HEMA), 2,3-epoxypropyl methacrylate (GMA), 2,3-dihydroxypropyl methacrylate (GOMA), and acrylamide (AAm) were used. The kinetics of the grafting reactions were examined, and the distribution of the graft component inside the trunk polymer was investigated by means of infrared (IR) spectroscopy. Surface-grafted as well as bulk- and surface-grafted products could be obtained. The mechanical behavior of the grafted films--especially in the water-swollen state--was examined and compared with that of the pure trunk polymer. In nearly all cases it was found that the tensile strength sigma B and the elongation at break epsilon R decreases as the grafting yield increases. Modification of GMA- and AAm-grafted films via chemical reactions was performed to create new functional groups of biomedical interest. In this manner a diol structure, a carboxylic acid structure, and a sulfonic acid group could be introduced in the grafted polymer. The water uptake of such modified films is increased markedly when compared with that of the unmodified samples.

  1. Radiation-induced grafting of acrylic acid onto polypropylene film and its biodegradability

    NASA Astrophysics Data System (ADS)

    Mandal, Dev K.; Bhunia, Haripada; Bajpai, Pramod K.; Chaudhari, C. V.; Dubey, K. A.; Varshney, L.

    2016-06-01

    Polypropylene based commodity polyolefins are widely used in packaging, manufacturing, electrical, pharmaceutical and other applications. The aim of the present work is to study the effect of grafting of acrylic acid on the biodegradability of acrylic acid grafted polypropylene. The effect of different conditions showed that grafting percentage increased with increase in monomer concentration, radiation dose and inhibitor concentration but decreased with increase in radiation dose rate. The maximum grafting of 159.4% could be achieved at optimum conditions. The structure of grafted polypropylene films at different degree of grafting was characterized by EDS, FTIR, TGA, DSC, SEM and XRD. EDS studies showed that the increase in acrylic acid grafting percentage increased the hydrophilicity of the grafted films. FTIR studies indicated the presence of acrylic acid on the surface of polypropylene film. TGA studies revealed that thermal stability decreased with increase in grafting percentage. DSC studies showed that melting temperature and crystallinity of the grafted polypropylene films lower than polypropylene film. SEM studies indicated that increase in acrylic acid grafting percentage increased the wrinkles in the grafted films. The maximum biodegradability could be achieved to 6.85% for 90.5% grafting. This suggested that microorganisms present in the compost could biodegrade acrylic acid grafted polypropylene.

  2. Development of hydrogels by radiation induced polymerization for use in slow drug delivery

    NASA Astrophysics Data System (ADS)

    Singh, Baljit; Bala, R.

    2014-10-01

    In the present work, in order to improve the drug release profile of indinavir sulfate, a potent inhibitor of HIV protease, controlled drug delivery systems in the form of hydrogels have been designed by a radiation graft polymerization method. These hydrogels have been prepared by using dietary fiber psyllium and binary monomers mixture of acrylamide (AAm) and 2-acrylamido-2-methylpropanesulfonic acid (AMPSA). These polymers have been characterized with cryo-SEMs, FTIR, XRD and swelling studies. The swelling of hydrogels has been determined in solution of different pH, temperature and [NaCl]. in vitro release studies of model drug indinavir sulfate in different pH have been carried out to determine the drug release mechanism. The release of dug occurred through non-Fickian mechanism.

  3. Towards application of one- and two-dimensional nanomaterials for reinforcement of polymeric nanocomposite bone grafts

    NASA Astrophysics Data System (ADS)

    Farrshid, Behzad

    One- and two-dimensional (1-D and 2-D) nanomaterials possess extraordinary physiochemical properties such as large surface area, excellent mechanical properties, high surface energy and good dispersivity in organic and biological solvents, therefore, they have been extensively used as reinforcing agents to improve the mechanical properties of polymeric scaffolds for bone tissue engineering applications. Carbon nanomaterials such as carbon nanotubes and graphene have been used as reinforcing agents for biodegradable polymeric scaffolds and composites, however, their short- and long-term in vitro cytotoxicity and in vivo biocompatibility is an area of extensive debate. In this study, we have systematically investigated the effects of addition of low concentrations (0.01-0.2 wt. %) of 1-D and 2-D carbon nanomaterials (graphene oxide nanoplatelets, graphene oxide nanoribbons and carbon nanotubes) and inorganic nanomaterials (boron nitride nanotubes, boron nitride nanoplatelers, tungsten disulfide nanotubes and molybdenum disulfide nanoplatelets) on the mechanical properties, cytocompatibility, and bioactivity of poly(propylene fumarate) (PPF) nanocomposites towards their potential applications as porous and nonporous implants for bone tissue engineering. Addition of nanomaterials in the PPF matrix improved the compressive and flexural mechanical properties of non-porous crosslinked PPF nanocomposites and porous PPF scaffolds. Our results suggest that in addition to high surface roughness and surface area of the nanomaterials, the presence of functional groups on the surface of nanomaterials leads to an increased nanomaterial-polymer interaction and a uniform dispersion of nanomaterials in polymer matrix which may be the key factors responsible for an improved mechanical reinforcement. The in vitro studies showed an excellent cytocompatibility for both carbon and inorganic nanomaterial reinforced PPF nanocomposites and scaffolds. Protein adsorption studies and in vitro

  4. Synthesis and characterization of N-vinylcaprolactam/N,N-dimethylacrylamide grafted onto chitosan networks by gamma radiation

    NASA Astrophysics Data System (ADS)

    Pérez-Calixto, M. P.; Ortega, A.; Garcia-Uriostegui, L.; Burillo, G.

    2016-02-01

    N-vinylcaprolactam (NVCL) and N,N-dimethylacrylamide (DMAAm) were grafted onto crosslinked chitosan by gamma radiation, using direct and indirect (pre-irradiation oxidative) methods. The binary graft systems were synthesized in one and two steps to evaluate the influences of architecture on the properties of the polymeric material. Maximum grafting percentages were obtained by the direct method. The different systems obtained were characterized by FTIR and TGA. The equilibrium swelling time of the (net-CS)-g-NVCL/DMAAm and [(net-CS)-g-NVCL]-g-DMAAm systems was 75 and 25 min, respectively, while crosslinked CS required about 24 h. Thermal and pH sensitivity were conserved in all systems; the pH response in [(net-CS)-g-NVCL]-g-DMAAm (LCST: 37°, pH: 5.2) is more defined than (net-CS)-g-NVCL/DMAAm (LCST: 37 °C, pH: 3.8). Grafting radiation showed to be an effective technique to modify CS hydrogels.

  5. Enhancement of the grafting performance and of the water absorption of cassava starch graft copolymer by gamma radiation

    NASA Astrophysics Data System (ADS)

    Kiatkamjornwong, Suda; Meechai, Nispa

    1997-06-01

    Enhancement of the gamma radiation grafting of acrylonitrile onto gelatinized cassava starch was investigated. Infrared spectrometry was used to follow the chemical changes in the grafting reaction and from saponification. The saponified starch- g-PAN (HSPAN) was then characterized in terms of grafting parameters to provide a guide for the optimum total dose (kGy) and the appropriate ratio of starch/acrylonitrile for a fixed dose rate of 2.5 × 10 -1 kGy/min. Other dose rates were also carried out to obtain the appropriate result of grafting copolymerization and of water absorption. A thin aluminium foil, covering the inner wall of the reaction vessel, was found to be far more effective than any other metal films in the enhancement of the grafting reaction and the water absorption as well. Nitric acid in the medium increases the grafting yield and the water absorption. Methyl ether hydroquinone inhibitor was evaluated for its ability to increase homopolymerization and decrease graft reaction. When styrene was used as a comonomer, it hampered the grafting of acrylonitrile onto starch backbone. The water absorption capacity was improved by freeze-drying the HSPAN. The treatment of the HSPAN with aluminium trichloride hexahydrate was found to enhance the degree of wicking, but to decrease the water absorbency.

  6. Functionalization of cotton fabrics by radiation induced grafting of quaternary salt to impart antibacterial property

    NASA Astrophysics Data System (ADS)

    Goel, N. K.; Kumar, Virendra; Rao, M. S.; Bhardwaj, Y. K.; Sabharwal, S.

    2011-11-01

    High energy gamma radiation has been used to covalently link polymer chains of a quaternary ammonium salt containing monomer, viz. [2-(Acryloyloxyethyl)]trimethylammonium chloride (AETC) to cotton fabric by mutual radiation grafting using 2-hydroxyethyl methacrylate (2-HEMA) monomer as the grafting facilitator. Grafting yield was found to increase with the radiation dose and monomer concentration. The grafted samples have been characterized for water uptake, surface morphology and thermal stability and for their antibacterial efficacy against various bacteria and were found to possess significant antibacterial activity particularly against gram-positive bacteria.

  7. UV-induced graft polymerization of acrylic acid in the sub-micronchannels of oxidized PET track-etched membrane

    NASA Astrophysics Data System (ADS)

    Korolkov, Ilya V.; Mashentseva, Anastassiya A.; Güven, Olgun; Taltenov, Abzal A.

    2015-12-01

    In this article, we report on functionalization of track-etched membrane based on poly(ethylene terephthalate) (PET TeMs) oxidized by advanced oxidation systems and by grafting of acrylic acid using photochemical initiation technique for the purpose of increasing functionality thus expanding its practical application. Among advanced oxidation processes (H2O2/UV) system had been chosen to introduce maximum concentration of carboxylic acid groups. Benzophenone (BP) photo-initiator was first immobilized on the surfaces of cylindrical pores which were later filled with aq. acrylic acid solution. UV-irradiation from both sides of PET TeMs has led to the formation of grafted poly(acrylic acid) (PAA) chains inside the membrane sub-micronchannels. Effect of oxygen-rich surface of PET TeMs on BP adsorption and subsequent process of photo-induced graft polymerization of acrylic acid (AA) were studied by ESR. The surface of oxidized and AA grafted PET TeMs was characterized by UV-vis, ATR-FTIR, XPS spectroscopies and by SEM.

  8. Radiation-grafted, chemically modified membranes part I - Synthesis of a selective aluminum material

    NASA Astrophysics Data System (ADS)

    Bazante-Yamaguishi, Renata; Moura, Eduardo; Manzoli, José E.; Geraldo, Aurea B. C.

    2014-01-01

    Polymeric membranes were styrene grafted by irradiation methods and the obtained material was chemically modified to become aluminum selective. For this purpose, polymeric substrates of PVC (polyvinyl chloride) and PP (polypropylene) were styrene grafted mutually by gamma and electron beam irradiation. The modification process includes three basic reaction paths: Friedel-Crafts acylation, 2-methylanisole coupling and a final oxidation to achieve aluminum selectivity. Although this specific chemical modification in derivatives of polystyrene is not new, the new challenge is to obtain a selective material where original membrane characteristics (physical shape and mechanical resistance) are minimally conserved after such an aggressive treatment.

  9. A review of radiation-grafted polymer electrolyte membranes for alkaline polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, Tianchi; Shao, Rong; Chen, Song; He, Xuemei; Qiao, Jinli; Zhang, Jiujun

    2015-10-01

    The past two decades have witnessed many efforts to develop radiation-grafted alkaline membranes for alkaline PEM fuel cell applications, as such membranes have certain advantages over other kinds of alkaline membranes, including well-controlled composition, functionality, and other promising properties. To facilitate research and development in this area, the present paper reviews radiation-grafted alkaline membranes. We examine their synthesis/fabrication/characterization, membrane material selection, and theoretical approaches for fundamental understanding. We also present detailed examinations of their application in fuel cell in terms of the working principles of the radiation grafting process, the fabrication of MEAs using radiation-grafted membranes, the membranes' corresponding performance in alkaline PEM fuel cells, as well as performance optimization. The paper also summarizes the challenges and mitigation strategies for radiation-grafted alkaline membranes and their application in PEM fuel cells, presenting an overall picture of the technology as it presently stands.

  10. Radiation graft modification of ethylene-propylene rubber—II. Effect of additives

    NASA Astrophysics Data System (ADS)

    Haddadi-Asl, V.; Burford, R. P.; Garnett, J. L.

    1995-02-01

    The effect of multifunctional acrylic additives including TMPTA, PEGDA and PGTA on the radiation grafting of hydrophilic vinyl monomers onto ethylene—propylene elastomer (EPM rubbers) was studied. This work centres upon gamma irradiation-induced grafting of acrylamide (AAm), N-vinyl-2-pyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA) and acrylonitrile (AN) onto EPM rubber by the simultaneous method. Water proved to be an effective solvent but methanol lowered grafting. Sulphuric acid was detrimental to both homopolymerisation and grafting, a result consistent with the theory proposed for the role of this additive in polymer grafting systems.

  11. Transparent Metal-Salt-Filled Polymeric Radiation Shields

    NASA Technical Reports Server (NTRS)

    Edwards, David; Lennhoff, John; Harris, George

    2003-01-01

    "COR-RA" (colorless atomic oxygen resistant -- radiation shield) is the name of a transparent polymeric material filled with x-ray-absorbing salts of lead, bismuth, cesium, and thorium. COR-RA is suitable for use in shielding personnel against bremsstrahlung radiation from electron-beam welding and industrial and medical x-ray equipment. In comparison with lead-foil and leaded-glass shields that give equivalent protection against x-rays (see table), COR-RA shields are mechanically more durable. COR-RA absorbs not only x-rays but also neutrons and rays without adverse effects on optical or mechanical performance. The formulation of COR-RA with the most favorable mechanical-durability and optical properties contains 22 weight percent of bismuth to absorb x-rays, plus 45 atomic percent hydrogen for shielding against neutrons.

  12. Boron Nitride Nanosheets (BNNSs) Chemically Modified by "Grafting-From" Polymerization of Poly(caprolactone) for Thermally Conductive Polymer Composites.

    PubMed

    Lee, Jinseong; Jung, Haejong; Yu, Seunggun; Man Cho, Suk; Tiwari, Vimal K; Babu Velusamy, Dhinesh; Park, Cheolmin

    2016-07-01

    To meet the growing demand for rapid heat dissipation in electronic devices to ensure their reliable performance with a high level of safety, many polymer composites with thermally conductive but electrically insulating 2D boron nitride nanosheets (BNNSs) are being developed. Here we present an efficient way to enhance the thermal conductivity (TC) of a polymer composite by means of "grafting-from" polymerization of a poly(caprolactone) (PCL) onto BNNSs. The BNNSs, which were exfoliated from bulk BN by means of ultra-sonication, were prepared by means of radical oxidation. These oxidized BNNSs (oxi-BNNSs) were employed as initiators for subsequent ring-opening polymerization of PCL, which successfully resulted in PCL chemically grafted onto BNNSs (PCL-g-BNNSs). The excellent dispersion of PCL-g-BNNSs in common solvents allowed us to readily fabricate a polymer composite that contained PCL-g-BNNSs embedded in a PCL matrix, and the composite showed TC values that were five and nine times greater in the out-of-plane and in-plane mode, respectively, than those of pristine PCL. PMID:27283727

  13. Thermo-responsive wound dressings by grafting chitosan and poly(N-isopropylacrylamide) to plasma-induced graft polymerization modified non-woven fabrics

    NASA Astrophysics Data System (ADS)

    Chen, Jyh-Ping; Kuo, Chang-Yi; Lee, Wen-Li

    2012-12-01

    To obtain a chitosan wound dressings with temperature-responsive characteristics, polypropylene (PP) non-woven fabric (NWF) was modified by direct current pulsed oxygen plasma-induced grafting polymerization of acrylic acid (AAc) to improve hydrophilicity and to introduce carboxylic acid groups. Conjugation of chitosan and poly(N-isopropylacrylamide) (PNIPAAm) followed by using water-soluble carbodiimide as a coupling agent to form a novel bigraft PP-g-chitosan-g-PNIPAAm wound dressing. The amount of chitosan and PNIPAAm grafted to PP-g-chitosan-g-PNIPAAm were 83.0 ± 4.6 μg/cm2 and 189.5 ± 8.2 μg/cm2, respectively. The surface chemical composition and microstructure of the NWF were studied by electron spectroscopy for chemical analysis (ESCA) and scanning electron microscopy (SEM). The linkages between AAc, chitosan, and PNIPAAm were confirmed with the formation of amide bonds. Physical properties of the NWF were characterized and potentials of these NWFs as wound dressings were evaluated using SD rat as the animal model. NWFs contained PNIPAAm were better than those contained only chitosan in wound healing rates and the wound areas covered by PP-g-chitosan-g-PNIPAAm wound dressings healed completely in 17 days.

  14. Effect of UV-irradiation intensity on graft polymerization of 2-methacryloyloxyethyl phosphorylcholine on orthopedic bearing substrate.

    PubMed

    Kyomoto, Masayuki; Moro, Toru; Yamane, Shihori; Hashimoto, Masami; Takatori, Yoshio; Ishihara, Kazuhiko

    2014-09-01

    Photoinduced grafting of 2-methacryloyloxyethyl phosphorylcholine (MPC) onto cross-linked polyethylene (CLPE) was investigated for its ability to reduce the wear of orthopedic bearings. We investigated the effect of UV-irradiation intensity on the extent of poly(MPC) (PMPC) grafting, and found that it increased with increasing intensity up to 7.5 mW/cm(2), and the remained fairly constant. It was found to be extremely important to carefully control the UV intensity, as at higher values, a PMPC gel formed via homopolymerization of the MPC, resulting in the formation of cracks at the interface of the PMPC layer and the CLPE substrate. When the CLPE was exposed to UV-irradiation during the graft polymerization process, some of its physical and mechanical properties were slightly changed due to cross-linking and scission effects in the surface region; however, the results of all of the tests exceed the lower limits of the ASTM standards. Modification of the CLPE surface with the hydrophilic PMPC layer increased lubrication to levels that match articular cartilage. The highly hydrated thin PMPC films mimicked the native cartilage extracellular matrix that covers synovial joint surface, acting as an extremely efficient lubricant, and providing high-wear resistance. PMID:24124003

  15. Radiation-grafting of acrylamide onto silicone rubber films for diclofenac delivery

    NASA Astrophysics Data System (ADS)

    Magaña, Hector; Palomino, Kenia; Cornejo-Bravo, Jose M.; Alvarez-Lorenzo, Carmen; Concheiro, Angel; Bucio, Emilio

    2015-02-01

    This work focuses on the pre-irradiation grafting of acrylamide (AAm) onto silicone rubber films (SR) and evaluates the effect of gamma-ray radiation conditions on the grafting yield, which in turn may influence the performance of the grafted materials as components of drug-eluting devices. Pristine and modified SR were characterized using FTIR-ATR, DSC, TGA, swelling, and water contact angle analysis in order to elucidate the effects of AAm grafting onto SR. Grafted films with content in AAm ranging from 0.81% to 22.20% showed excellent cytocompatibility against fibroblasts, and capability to uptake the anti-inflammatory drug diclofenac. Amount of drug loaded directly correlated with the grafting degree of the films. Drug release studies were performed at pH 7.4 and 37 °C (physiological conditions). Most grafted films released the drug in a sustained way for at least three hours.

  16. Novel Diblock Copolymer-Grafted Multiwalled Carbon Nanotubes via a combination of Living and Controlled/Living Surface Polymerizations

    SciTech Connect

    Priftis, Dimitrios; Sakellariou, Georgios; Mays, Jimmy; Hadjichristidis, Nikos

    2010-01-01

    Diels Alder cycloaddition reactions were used to functionalize multiwalled carbon nanotubes (MWNTs) with 1-benzocylcobutene-10-phenylethylene (BCB-PE) or 4-hydroxyethylbenzocyclobutene (BCB-EO). The covalent functionalization of the nanotubes with these initiator precursors was verified by FTIR and thermogravimetric analysis (TGA). After appropriate transformations/additions, the functionalized MWNTs were used for surface initiated anionic and ring opening polymerizations of ethylene oxide and e-caprolactone (e-CL), respectively. The OH-end groups were transformed to isopropylbromide groups by reaction with 2-bromoisobutyryl bromide, for subsequent atom transfer radical polymerization of styrene or 2-dimethylaminoethyl methacrylate to afford the final diblock copolymers. 1H NMR, differential scanning calorimetry (DSC), TGA, and transmission electron microscopy (TEM) were used for the characterization of the nanocomposite materials. TEM images showed the presence of a polymer layer around the MWNTs as well as the dissociation of MWNT bundles. Consequently, this general methodology, employing combinations of different polymerization techniques, increases the diversity of diblocks that can be grafted from MWNTs.

  17. Industrialization of radiation-induced emulsion polymerization ----technological process and its advantages

    NASA Astrophysics Data System (ADS)

    Zhicheng, Zhang; Manwei, Zhang

    1993-07-01

    A technological process for industrialization of radiation induced emulsion polymerization was introduced briefly. A batch process rather than continuous one was adopted in the industrial-scale production. The advantages of radiation induced emulsion polymerization were described in comparison with chemical initiated process.

  18. Photochemical modification of poly(ether sulfone) ultrafiltration membranes by UV-assisted graft polymerization for the prevention of biofouling

    NASA Astrophysics Data System (ADS)

    Pieracci, John Paul

    Membranes are widely used by the biotechnology industry in the separation and recovery of proteins from biological solutions. Fouling of membrane surfaces by irreversible protein adsorption during ultrafiltration causes loss of membrane permeability and can reduce membrane selectivity and lead to significant product loss through denaturation. In this work, low fouling poly(ether sulfone) (PES) ultrafiltration membranes were produced by ultraviolet (UV) assisted graft polymerization of hydrophilic vinyl monomers using a newly developed photochemical dip modification technique. This technique was developed to make the UV modification process more easily adaptable to continuous membrane manufacturing processes. A method was also developed to measure and track the degree of polymer grafting on the membrane surface using attenuated total reflection Fourier transform infrared spectroscopy (FTIR/ATR). Grafting the hydrophilic monomer N-vinyl-2-pyrrolidinone (NVP) onto the membrane surface increased surface wettability and produced membranes with the high wettability of regenerated cellulose membranes. The enhanced surface wettability significantly decreased irreversible adsorptive fouling during the filtration of the protein bovine serum albumin (BSA). In order to maintain the rejection of BSA after modification, PES chain scission was tightly controlled by regulating the UV wavelength range and the light intensity used. The UV reactor system was operated with 300 nm UV lamps and a benzene filter used to remove high energy wavelengths below 275 nm that were determined to cause severe loss of BSA rejection due to pore enlargement from extensive chain scission. Dip modification caused membrane permeability to decrease due to the grafted chains blocking the membrane pores. The use of a chain transfer agent during modification followed by ethanol cleaning increased modified membrane permeability, but BSA rejection was severely decreased. The resultant membranes produced by

  19. Radiation-induced polymerization for the immobilization of penicillin acylase

    SciTech Connect

    Boccu, E.; Carenza, M.; Lora, S.; Palma, G.; Veronese, F.M.

    1987-06-01

    The immobilization of Escherichia coli penicillin acylase was investigated by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperature. A leak-proof composite that does not swell in water was obtained by adding the cross-linking agent trimethylolpropane trimethacrylate to the monomer-aqueous enzyme mixture. Penicillin acylase, which was immobilized with greater than 70% yield, possessed a higher Km value toward the substrate 6-nitro-3-phenylacetamidobenzoic acid than the free enzyme form (Km = 1.7 X 10(-5) and 1 X 10(-5) M, respectively). The structural stability of immobilized penicillin acylase, as assessed by heat, guanidinium chloride, and pH denaturation profiles, was very similar to that of the free-enzyme form, thus suggesting that penicillin acylase was entrapped in its native state into aqueous free spaces of the polymer matrix.

  20. Influence of gamma radiation onto polymeric matrix with papain

    NASA Astrophysics Data System (ADS)

    Zulli, Gislaine; Lopes, Patrícia Santos; Velasco, Maria Valéria Robles; Alcântara, Mara Tânia Silva; Rogero, Sizue Ota; Lugao, Ademar Benévolo; Mathor, Monica Beatriz

    2010-03-01

    Papain is a proteolytic enzyme that has been widely used as debridement agent for scars and wound healing treatment. However, papain presents low stability, which limits its use to extemporaneous or short shelf-life formulations. The purpose of this study was to entrap papain into a polymeric matrix in order to obtain a drug delivery system that could be used as medical device. Since these systems must be sterile, gamma radiation is an interesting option and presents advantages in relation to conventional agents: no radioactive residues are formed; the product can be sterilized inside the final packaging and has an excellent reliability. The normative reference for the establishment of the sterilizing dose determines 25 kGy as the inactivation dose for viable microorganisms. A silicone dispersion was selected to prepare membranes containing 2% (w/w) papain. Irradiated and non-irradiated membranes were simultaneously assessed in order to verify whether gamma radiation interferes with the drug-releasing profile. Results showed that irradiation does not affect significantly papain release and its activity. Therefore papain shows radioresistance in the irradiation conditions applied. In conclusion, gamma radiation can be easily used as sterilizing agent without affecting the papain release profile and its activity onto the biocompatible device is studied.

  1. Synergistic-radiation grafting: A novel modification technique for the preparation of biomaterials

    NASA Astrophysics Data System (ADS)

    Müller-Schulte, D.

    1993-10-01

    Radiation grafting was performed using different vinylmonomers and solvents simultaneously to modify polyamide-6 substrates. With the new technique, immunadsorbents and media for affinity chromatography were developed for the separation of low density lipoproteins, IgG antibodies and biotin- antibodies. To increase the biocompatibility of polymers, a graft modification was applied which allowed a totally coherent endothelial cell seeding.

  2. Electrodialysis of Sulfuric Acid with Cation-Exchange Membranes Prepared by Electron-Beam-Induced Graft Polymerization

    NASA Astrophysics Data System (ADS)

    Asari, Yuki; Shoji, Nobuyoshi; Miyoshi, Kazuyoshi; Umeno, Daisuke; Saito, Kyoichi

    Strongly acidic cation-exchange membranes were prepared by the electron-beam-induced graft polymerization of glycidyl methacrylate onto a high-density polyethylene film with a thickness of 35 μm and the subsequent conversion of the resulting epoxy group into a sulfonic acid group. The resulting cation-exchange membranes with various ion-exchange capacities or sulfonic acid group densities ranging from 1.9 to 2.7 mmol/g were applied to the enrichment of 0.50 mol/L sulfuric acid by electrodialysis. Concentrated sulfuric acids at concentrations of 1.4 to 2.9 mol/L were obtained in the concentrate chamber during the electrodialysis operated at 30 mA/cm2 and 298 K, using a pair of this cation-exchange membrane and a commercially available anion-exchange membrane.

  3. Radical graft polymerization of an Allyl Monomer onto Hydrophilic Polymers and their antibacterial nanofibrous membranes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Hydrophilic poly (vinyl alcohol-co-ethylene) (PVA-co-PE) copolymers with 27 mol %, 32 mol % and 44 mol % ethylene were functionalized by melt radical graft copolymerization with 2,4-diamino-6-diallylamino-1,3,5-triazine (NDAM) using reactive extrusion. This functionalization imparts antibacterial pr...

  4. Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane) Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol.

    PubMed

    Saito, Kei; Miyamoto, Koji; Nanayakkara, Sepa; Ihara, Hirotaka; Hearn, Milton T W

    2016-01-01

    A new solid phase catalyst, poly(N-4-vinylbenzyl-1,4,7-triazacyclononane) copper(I) complex, grafted onto polystyrene particles, has been employed for the oxidative polymerization of 2,6-dimethylphenol using an aqueous biphasic (water/toluene) solvent system. The solid catalyst was synthesized by first grafting N-(4-vinylbenzyl)-1,4,7-triaza-cyclononane onto polystyrene particles using a radical mediated polymerization method and next by creating the polymer-metal complex of copper-triazacyclononane with these modified particles. Poly(2,6-dimethyl-1,4-phenylene oxide) was successfully obtained from the polymerization of 2,6-dimethylphenol using this new metal-organic solid phase catalyst. PMID:26821005

  5. Grafting Poly(ethylene glycol) Onto Single-Walled Carbon Nanotubes by Living Anionic Ring-Opening Polymerization.

    PubMed

    Li, Wei; Zhang, Guoxiang; Sheng, Wenbo; Liu, Zhiyong; Jia, Xin

    2016-01-01

    Recent years, many methods have been developed to widen the practical application of single-walled carbon nanotubes (SWCNTs). Among them, PEGylation is a general strategy to endow functionality, biocompatibility as well as its good solubility. In this paper, poly(ethylene glycol) (PEG) is successfully grafted onto SWCNTs through living anionic ring-opening polymerization of ethylene oxide (EO). By controlling the amount of monomer and initiator, a series of PEGylated SWCNTs with different PEG molecular weight and density are prepared. Then, the as-prepared SWCNTs have been verified by thermogravimetric analyses (TGA), Raman spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS). Finally, the protein resistance property of the PEGylated SWCNTs is investigated. It is found that these PEGylated SWCNTs have a good protein resistance property and the higher the content of PEG grafted on the SWCNTs, the less adsorption amount of BSA and the larger capacity to resist protein absorption. This work provides a novel method to prepare PEGylated SWCNTs. PMID:27398490

  6. Biodegradability of poly(3-hydroxybutyrate) film grafted with vinyl acetate: Effect of grafting and saponification

    NASA Astrophysics Data System (ADS)

    Wada, Yuki; Seko, Noriaki; Nagasawa, Naotsugu; Tamada, Masao; Kasuya, Ken-ichi; Mitomo, Hiroshi

    2007-06-01

    Radiation-induced graft polymerization of vinyl acetate (VAc) onto poly(3-hydroxybutyrate) (PHB) film was carried out. At a degree of grafting higher than 5%, the grafted films (PHB-g-VAc) completely lost the enzymatic degradability that is characteristic of PHB due to the grafted VAc covering the surface of the PHB film. However, the biodegradability of the PHB-g-VAc films was recovered when the films were saponified in alkali solution under optimum conditions. Graft chains of the PHB-g-VAc film reacted selectively to become biodegradable polyvinyl alcohol (PVA). The biodegradability of the saponified PHB-g-VAc film increased rapidly with time.

  7. Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane surface with stably anti-protein-fouling performance via a two-step surface polymerization

    NASA Astrophysics Data System (ADS)

    Li, Qian; Bi, Qiu-Yan; Zhou, Bo; Wang, Xiao-Lin

    2012-03-01

    A zwitterionic polymer, poly(3-(methacryloylamino) propyl-dimethyl-(3-sulfopropyl) ammonium hydroxide) (poly(MPDSAH)) was successfully grafted in high density from the surface of poly(vinylidene fluoride) (PVDF) hollow fiber membrane via a two-step polymerization. Poly(2-hydroxyethyl methacrylate) (poly(HEMA)) chains were firstly grafted from outside surface of PVDF membrane through atom transfer radical polymerization (ATRP) to provide the initiation sites for subsequent cerium (Ce (IV))-induced graft copolymerization of polyMPDSAH in the presence of N,N'-ethylene bisacrylamide (EBAA) as a cross-linking agent. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) confirmed that the EBAA could stimulate zwitterionic polymers grafting onto the membrane surface. The dense poly(MPDSAH) layers on the PVDF membrane surface were revealed by the scanning electron microscope (SEM). The mechanical property of PVDF membrane was improved by the zwitterionic surface layers. The gravimetry results indicated the grafting amount increased to 520 μg/cm2 for a copolymerization time of more than 3 h. Static and dynamic water contact angle measurements showed that the surface hydrophilicity of the PVDF membranes was significantly enhanced. As the grafting amount reached 513 μg cm-2, the value of contact angle dropped to 22.1° and the amount of protein adsorption decreased to zero. The cyclic experiments for BSA solution filtration demonstrated that the extent of protein fouling was significantly reduced and most of the fouling was reversible. The grafted polymer layer on the PVDF membrane showed a good stability during the membrane cleaning process. The experimental results concluded a good prospect in obtaining the sulfobetaine-modified PVDF membranes with high mechanical strength, good anti-protein-fouling performance, and long-term stability via the two-step polymerization.

  8. Polymeric Prodrug Grafted Hollow Mesoporous Silica Nanoparticles Encapsulating Near-Infrared Absorbing Dye for Potent Combined Photothermal-Chemotherapy.

    PubMed

    Zhang, Yuanyuan; Ang, Chung Yen; Li, Menghuan; Tan, Si Yu; Qu, Qiuyu; Zhao, Yanli

    2016-03-23

    In this study, polymeric prodrug coated hollow mesoporous silica nanoparticles (HMSNs) with encapsulated near-infrared (NIR) absorbing dye were prepared and explored for combined photothermal-chemotherapy. A copolymer integrated with tert-butoxycarbonyl protected hydrazide groups and oligoethylene glycols was initially grafted on the surface of HMSNs via reversible addition-fragmentation chain-transfer (RAFT) polymerization followed by the deprotection to reactivate the hydrazide groups for the conjugation of anticancer drug doxorubicin (DOX). DOX was covalently bound onto the polymer substrate by acid-labile hydrazone bond and released quickly in weak acidic environment for chemotherapy. The hollow cavity of HMSNs was loaded with an NIR absorbing dye IR825 to form the final multifunctional hybrid denoted as HMSNs-DOX/IR825. The hybrid exhibited good dispersity and stability as well as high light-to-heat conversion efficiency. As revealed by confocal microscopy and flow cytometry analysis, the hybrid was efficiently taken up by cancer cells, and the conjugated DOX could be released under the cellular environment. In vitro cytotoxicity study demonstrated that anticancer activity of HMSNs-DOX/IR825 could be significantly improved by the NIR irradiation, which led to a satisfactory therapeutic efficacy through the combination treatment. Thus, the developed hybrid could be a promising candidate for the combined photothermal-chemotherapy of cancer. PMID:26937591

  9. Gamma radiation-induced grafting of acrylamide and dimethyl diallyl ammonium chloride onto starch.

    PubMed

    Lv, Xiaohua; Song, Weiqiang; Ti, Yongzhou; Qu, Lingbo; Zhao, Zhiwei; Zheng, Hongjuan

    2013-01-30

    Corn starch graft copolymers were prepared from acrylamide/dimethyl diallyl ammonium chloride binary monomers (AM/DMDAAC) by a simultaneous radiation grafting method, and were characterized by FTIR and (1)H NMR techniques, weight measurement and titration method. The copolymers with high grafting ratio and high grafting efficiency of binary monomers were achieved at absorbed doses of 2 kGy and 3 kGy using a 6:9.8:4.2 (w/w/w) ratio of starch/AM/DMDAAC, but their cationic degrees were low. Grafting ratio, grafting efficiency and cationic degree of the copolymers increased with increasing AM content in comonomer mixtures and then decreased at 3kGy using a 6:14 ratio of starch:total comonomers, but their cationic degrees generally decreased with increasing AM content. The grafting ratio, the grafting efficiency and the cationic degree of the copolymers increased, but the grafting efficiency of DMDAAC decreased with varying starch/(AM+DMDAAC) ratio from 6:3 to 6:18 at 3 kGy by using a fixed 7:3 ratio of AM:DMDAAC. PMID:23218310

  10. Hybrid Nanomaterials by Surface Grafting of Synthetic Polypeptides Using N-Carboxyanhydride (NCA) Polymerization.

    PubMed

    Borase, Tushar; Heise, Andreas

    2016-07-01

    The interaction of materials with their environment is largely dictated by interfacial phenomena. Polymers are very versatile materials to modulate material interfaces to provide functionality, stability and compatibility. A class of polymers that can close the gap between fully synthetic and natural macromolecules are polypeptides derived from N-carboxyanhydride (NCA) polymerization. Recent advances in using this technique to create biomimetic interfaces and hybrid materials are highlighted, with special emphasis on nanomaterials. PMID:26780161

  11. Surface-initiated Ring-opening Metathesis Polymerization in the Vapor Phase: An Efficient Method for Grafting Cyclic Olefins of Low Strain Energies

    PubMed Central

    Lerum, Maria Felisa Z.; Chen, Wei

    2011-01-01

    Surface grafting of cyclic olefins with low strain energies, including cyclopentene (CP), 1,4-cyclohexadiene (CHD), cycloheptene (CHP), cis-cyclooctene (CO), cis,cis-1,5-cyclooctadiene (COD), 1,3,5,7-cyclooctatetraene (COT), cyclododecene (CD), and trans,trans,cis-1,5,9-cyclododecatriene (CDT), were explored using ring-opening metathesis polymerization in the vapor phase. These monomers do not polymerize when SiROMP is carried out in solution due to pronounced chain transfer on surfaces where chains are in close proximities. In the vapor phase, however, chain transfer is suppressed at the solid-vapor interfaces, which permits the polymerization of most of these monomers. A minimal required strain energy of 2.2 kcal/mol was determined in this study, which is significantly lower than the estimated 13.3 kcal/mol for SiROMP carried out in solution, indicating that the enhancement in monomer polymerizability is significant using the vapor phase approach. A series of polyalkenamers with controlled fraction of unsaturation from 8% to 50% along the polymer backbone were grafted to solid substrates. It was observed that the logarithm of largest grafted layer thickness obtained before the removal of chain transfer products – which correlates with the extent of polymerization – scales with monomer strain energy. This confirms that the release of ring strain is the thermodynamic driving force for SiROMP. It was also found that although chain transfer is suppressed in the vapor phase, it is important in monomer/polymer systems where the fraction of unsaturated bonds is high. In these cases, grafted polymer thickness is dominated by chain transfer, rather than by monomer strain energy. A quantitative relationship is established for estimating graft thickness of a particular monomer using its strain energy and fraction of unsaturated bonds in the monomer. PMID:21469729

  12. Synthesis and Characterization of Surface Grafted Poly(N-isopropylacrylamide) and Poly(Carboxylic Acid)– Iron Particles via Atom Transfer Radical Polymerization for Biomedical Applications

    PubMed Central

    Sutrisno, Joko; Fuchs, Alan; Evrensel, Cahit

    2014-01-01

    This research relates to the preparation and characterization of surface grafted poly(N-isopropylacrylamide) and poly(carboxylic acid)–micron-size iron particles via atom transfer radical polymerization (ATRP). The surface grafted polymers–iron particles result in multifunctional materials which can be used in biomedical applications. The functionalities consist of cell targeting, imaging, drug delivery, and immunological response. The multifunctional materials are synthesized in two steps. First, surface grafting is used to place polymer molecules on the iron particles surface. The second step, is conjugation of the bio-molecules onto the polymer backbone. Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy were used to confirm the presence of polymers on the iron particles. The thickness of the grafted polymers and glass transition temperature of the surface grafted polymers were determined by transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The covalent bond between grafted polymers and iron particles caused higher glass transition temperature as compared with non-grafted polymers. The ability to target the bio-molecule and provide fluorescent imaging was simulated by conjugation of rat immunoglobulin and fluorescein isothiocyanate (FITC) labeled anti-rat. The fluorescence intensity was determined using flow cytometry and conjugated IgG-FITC anti-rat on iron particles which was imaged using a fluorescence microscopy. PMID:25382869

  13. Kinetics of a methyl methacrylate polymerization initiated by the stable free radicals in irradiated polytetrafluoroethylene and properties of the resultant graft polymer

    SciTech Connect

    Donato, K.A.E.

    1987-01-01

    The kinetics of the polymerization of methyl methacrylate (MMA) initiated by the stable free radicals in commercially available irradiated polytetrafluoroethylene micropowder and the rheological, thermal, chemical, and mechanical properties of the resultant graft polymer are described. Test tube runs using different ratios of MMA to PTFE were made to determine the feasibility of the reaction and optimum reaction conditions. The amount of graft produced was equal to the weight gain of the solids after removal of the adventitious homopolymer by extraction in acetone. Test quantities of material were produced in a 500 milliliter agitated reactor. A higher ratio of PTFE to excess MMA and longer reaction times result in higher conversion in test tubes. A kinetic model was developed to relate the original concentration of PTFE free radical to the amount of MMA polymer. Graft polymer containing PTFE micropowder, PMMA graft, and PMMA homopolymer in a ratio of 18:5:1 was used for property characterization. The graft material extrudes well at 513K and has a viscosity comparable to that of PMMA homopolymer. The material is stable upon re-extrusion. DSC thermograms show that the heat of transition of the PTFE melting peak is proportional to the amount of PTFE in the sample. Good solvents for PMMA are detrimental to the structural integrity of the graft extrudate; heat treatment improves the chemical resistance. The PTFE block controls the mechanical properties of the graft.

  14. Superabsorbent hydrogels via graft polymerization of acrylic acid from chitosan-cellulose hybrid and their potential in controlled release of soil nutrients.

    PubMed

    Essawy, Hisham A; Ghazy, Mohamed B M; El-Hai, Farag Abd; Mohamed, Magdy F

    2016-08-01

    Superabsorbent polymers fabricated via grafting polymerization of acrylic acid from chitosan (CTS) yields materials that suffer from poor mechanical strength. Hybridization of chitosan with cellulose (Cell) via chemical bonding using thiourea formaldehyde resin increases the flexibility of the produced hybrid (CTS/Cell). The hybridization process and post graft polymerization of acrylic acid was followed using Fourier transform infrared (FTIR). Also, the obtained structures were homogeneous and exhibited uniform surface as could be shown from imaging with scanning electron microscopy (SEM). Thus, the polymers derived from the grafting of polyacrylic acid from (CTS/Cell) gave rise to much more mechanically robust structures ((CTS/Cell)-g-PAA) that bear wide range of pH response due to presence of chitosan and polyacrylic acid in one homogeneous entity. Additionally, the obtained structures possessed greater water absorbency 390, 39.5g/g in distilled water and saline (0.9wt.% NaCl solution), respectively, and enhanced retention potential even at elevated temperatures as revealed by thermogravimetric analysis (TGA). This could be explained by the high grafting efficiency (GE%), 86.4%, and grafting yield (GY%), 750%. The new superabsorbent polymers proved to be very efficient devices for controlled release of fertilizers into the soil which expands their use in agriculture and horticultural applications. PMID:27126169

  15. Mucoadhesive thermo-responsive chitosan-g-poly(N-isopropylacrylamide) polymeric micelles via a one-pot gamma-radiation-assisted pathway.

    PubMed

    Sosnik, Alejandro; Imperiale, Julieta C; Vázquez-González, Brenda; Raskin, Maya Menaker; Muñoz-Muñoz, Franklin; Burillo, Guillermina; Cedillo, Gerardo; Bucio, Emilio

    2015-12-01

    Thermo-sensitive graft copolymer amphiphiles of chitosan (CS) and poly(N-isopropylacrylamide) (PNiPAAm), CS-g-PNIPAAm, were successfully synthesized by a catalyst-less one-pot gamma (γ)-radiation-assisted free radical polymerization at three different radiation doses: 5, 10 and 20 kGy. The chemical structure of the copolymers was confirmed by FTIR and solid-state (13)C NMR and the grafting extent by (1)H NMR and gravimetric analysis. In general, the higher the dose, the smaller the grafting due to the more significant NiPAAm homopolymerization. Due to the grafting of poly(NiPAAm) blocks, aqueous solutions of the different copolymers underwent a sharp transition upon heating above 32 °C, the characteristic lower critical solution temperature (LCST) of poly(NiPAAm). Then, the critical micellar concentration (CMC), the size and size distribution and the zeta-potential were characterized by dynamic light scattering (DLS) and the polymeric micelles visualized in suspension and quantified by Nanoparticle Tracking Analysis (NTA), at 37 °C. CMC values were in the 0.0012-0.0025%w/v range and micelles displayed sizes between 99 and 203 nm with low polydispersity (<0.160) and highly positive zeta-potential (>+15 mV) that suggested the partial conservation of the amine groups upon NiPAAm grafting. Consequently, polymeric micelles displayed the intrinsic mucoadhesiveness of CS, as established in vitro by the mucin solution assay. Finally, the encapsulation capacity of the micelles was assessed with the highly hydrophobic protease inhibitor antiretroviral indinavir free base (IDV). Polymeric micelles led to a significant 24-fold increase of the aqueous solubility from 63 μg/mL to 1.45 mg/mL, a performance remarkably better than different poly(ethylene oxide)-b-poly(propylene oxide) block copolymers assessed before. Overall results highlight the potential of this nanotechnology platform to expand the application of polymeric micelles to mucosal administration routes. PMID

  16. Polymer-grafted silica: A screening system for polymeric adsorption resin development

    SciTech Connect

    Browne, T.E.; Cohen, Y. )

    1993-04-01

    A screening-level methodology was developed for the evaluation of solute affinity for polymers that are candidate sorption resins. In this approach novel grafted polymer-silica resins were synthesized to produce poly(vinylpyrrolidone)-silica (PVP-Si) and poly(vinyl acetate)-silica (PVAc-Si) resins. The polymer-silica resins along with a number of commercially available polymer resins were used to evaluate the aqueous-phase adsorption of phenol, tetrachloroethene (PCE), trichloroethene (TCE), and chloroform. The polymer-grafted silicas were able to selectively remove pollutants from water with a covalently bonded polymer layer that has a high affinity for the target pollutant. The PVAc-silica resin had a sorption capacity for TCE and CHCl[sub 3] as high as commercial poly(styrene) resin XAD-4; the PVP-Si resin had a sorption capacity for phenol higher than a commercial poly-(vinylpyridine) resin (Reillex 425). PCE adsorption onto the PVAc-silica was comparable to the commercial poly(methacrylate) and poly(vinylpyridine) resins but less than the poly(styrene) resin. The results show that the Hildebrand solubility parameter along with the dipole moment of the polymer functional groups can be used for an initial screening-level assessment of polymer-solute affinity.

  17. Synthesis, modification and graft polymerization of magnetic nano particles for PAH removal in contaminated water

    PubMed Central

    2014-01-01

    Magnetic nanoparticles (MNPs) were modified with 3-Mercaptopropytrimethoxysiline (MPTMS) and grafted with allyl glycidyl ether for coupling with beta naphtol as a method to form a novel nano-adsorbent to remove two poly aromatic hydrocarbons (PAHs) from contaminated water. The modified MNPs were characterized by transmission electron microscopy, infrared spectroscopy and thermogravimetric analysis. Results showed that the modified MNPs enhanced the process of adsorption. Tests were done on the adsorption capacity of the two PAHs on grafted MNPs; factors applied to the tests were temperature, contact time, pH, salinity and initial concentration of PAHs. Results revealed that adsorption equilibrium was achieved in 10 min, and the maximum adsorption capacity was determined as 4.15 mg/g at pH = 7.0 and 20°C. The equilibrium adsorption data of the two PAHs by the modified MNPs were analyzed by Langmuir, Freundlich and Temkin models. Equilibrium adsorption data was determined from the Langmuir, Freundlich and Temkin constants from tests under conditions of pH = 7 and temperature 20°C. Analysis of the adsorption-desorption process indicated that the modified MNPs had a high level of stability and good reusability. Magnetic separation in these tests was fast and this shows that the modified MNPs have great potential to be used as a new adsorbent for the two PAHs removal from contaminated water in water treatment. PMID:25101170

  18. Immobilization of microbial cells on cellulose-polymer surfaces by radiation polymerization

    SciTech Connect

    Kumakura, M.; Kaetsu, I.

    1983-12-01

    Streptomyces phaeochromogens cells were immobilized on cellulose-polymer surfaces by radiation polymerization using hydrophilic monomers and paper. The enzyme activity of immobilized cell sheets was higher than that of immobilized cell composites obtained by the usual radiation polymerization technique. The enzyme activity of the sheets was affected by monomer concentration, the thickness of paper, and the degree of polymerization of paper. The copolymerization of hydroxyethyl methacrylate and methoxytetraethyleneglycol methacrylate in the sheets led to a further increase of the enzyme activity due to the increase of the hydrophilicity of the polymer matrix. The Michaelis constant of the sheets from low monomer concentration was close to that of intact cells.

  19. Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis Cells: Evaluation of Key Membrane Properties.

    PubMed

    Albert, Albert; Barnett, Alejandro O; Thomassen, Magnus S; Schmidt, Thomas J; Gubler, Lorenz

    2015-10-14

    Radiation-grafted membranes can be considered an alternative to perfluorosulfonic acid (PFSA) membranes, such as Nafion, in a solid polymer electrolyte electrolyzer. Styrene, acrylonitrile, and 1,3-diisopropenylbenzene monomers are cografted into preirradiated 50 μm ethylene tetrafluoroethylene (ETFE) base film, followed by sulfonation to introduce proton exchange sites to the obtained grafted films. The incorporation of grafts throughout the thickness is demonstrated by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis of the membrane cross-sections. The membranes are analyzed in terms of grafting kinetics, ion-exchange capacity (IEC), and water uptake. The key properties of radiation-grafted membranes and Nafion, such as gas crossover, area resistance, and mechanical properties, are evaluated and compared. The plot of hydrogen crossover versus area resistance of the membranes results in a property map that indicates the target areas for membrane development for electrolyzer applications. Tensile tests are performed to assess the mechanical properties of the membranes. Finally, these three properties are combined to establish a figure of merit, which indicates that radiation-grafted membranes obtained in the present study are promising candidates with properties superior to those of Nafion membranes. A water electrolysis cell test is performed as proof of principle, including a comparison to a commercial membrane electrode assembly (MEA). PMID:26393461

  20. Modification on liquid retention property of cassava starch by radiation grafting with acrylonitrile. I. Effect of γ-irradiation on grafting parameters

    NASA Astrophysics Data System (ADS)

    Kiatkamjornwong, S.; Chvajarernpun, J.; Nakason, C.

    1993-07-01

    Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85°C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to gamma-rays. A thin aluminum foil was used to cover the inner wall of the reaction vessel, so that the homopolymer concentration was reduced to be less than 1.0% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmation of graft copolymerization and saponification reactions was made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the total dose on the extent of the grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis.

  1. Preparation of Mg(OH)2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-02-01

    Mg(OH)2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)2 crystals and affect the formation of lamella-like Mg(OH)2 crystals. The cellulose fiber grafted with modified Mg(OH)2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  2. Effect of solvents on the radiation-induced polymerization of ethyl and isopropyl vinyl ethers

    SciTech Connect

    Hsieh, W.C.

    1981-01-01

    The effect of solvents on the radiation-induced cationic polymerization of ethyl and isopropyl vinyl ethers (EVE and IPVE, respectively) was investigated. EVE and IPVE polymerizations were carried out in bulk and in solution under superdry conditions in which polar impurities, especially water, have been reduced to negligible levels. This was accomplished by means of a sodium mirror technique using joint free baked out glass equipment and high vacuum. Plots of the monomer conversions and irradiation times were obtained for EVE and IPVE polymerizations in bulk and in benzene solution at constant monomer concentrations. The monomer concentration dependence of the polymerization rate was studied for EVE polymerization in bulk and in benzene, diethlyl ether, diglyme and methylene chloride, and for IPVE polymerization in bulk and in benzene. Solvent effect on the estimated propagating rate constants was examined for EVE and IPVE polymerization in bulk and in solution. The effect of temperature on the polymerization rate was also investigated for EVE polymerization in bulk ad in benzene, diethyl and diisopropyl ethers, methylene chloride and nitromethane, and for IPVE ploymerization in bulk and in benzene.

  3. Characterization of Bonding Between Poly(dimethylsiloxane) and Cyclic Olefin Coplymer Using Corona Discharge Induced Grafting Polymerization

    PubMed Central

    Liu, Ke; Gu, Pan; Hamaker, Kiri; Fan, Z. Hugh

    2011-01-01

    Thermoplastics have been increasingly used for fabricating microfluidic devices because of their low cost, mechanical/biocompatible attributes, and well-established manufacturing processes. However, there is sometimes a need to integrate such a device with components made from other materials such as polydimethylsiloxane (PDMS). Bonding thermoplastics with PDMS to produce hybrid devices is not straightforward. We have reported our method to modify the surface property of a cyclic olefin copolymer (COC) substrate by using corona discharge and grafting polymerization of 3-(trimethoxysilyl)propyl methacrylate; the modified surface enabled strong bonding of COC with PDMS. In this paper, we report our studies on the surface modification mechanism using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurement. Using this bonding method, we fabricated a three-layer (COC/PDMS/COC) hybrid device consisting of elastomer-based valve arrays. The microvalve operation was confirmed through the displacement of a dye solution in a fluidic channel when the elastomer membrane was pneumatically actuated. Valve-enabled microfluidic handling was demonstrated. PMID:21962541

  4. Characterization of bonding between poly(dimethylsiloxane) and cyclic olefin copolymer using corona discharge induced grafting polymerization.

    PubMed

    Liu, Ke; Gu, Pan; Hamaker, Kiri; Fan, Z Hugh

    2012-01-01

    Thermoplastics have been increasingly used for fabricating microfluidic devices because of their low cost, mechanical/biocompatible attributes, and well-established manufacturing processes. However, there is sometimes a need to integrate such a device with components made from other materials such as polydimethylsiloxane (PDMS). Bonding thermoplastics with PDMS to produce hybrid devices is not straightforward. We have reported our method to modify the surface property of a cyclic olefin copolymer (COC) substrate by using corona discharge and grafting polymerization of 3-(trimethoxysilyl)propyl methacrylate; the modified surface enabled strong bonding of COC with PDMS. In this paper, we report our studies on the surface modification mechanism using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurement. Using this bonding method, we fabricated a three-layer (COC/PDMS/COC) hybrid device consisting of elastomer-based valve arrays. The microvalve operation was confirmed through the displacement of a dye solution in a fluidic channel when the elastomer membrane was pneumatically actuated. Valve-enabled microfluidic handling was demonstrated. PMID:21962541

  5. Modification of nylon-6 fibres by radiation-induced graft polymerisation of vinylbenzyl chloride

    NASA Astrophysics Data System (ADS)

    Ting, T. M.; Nasef, Mohamed Mahmoud; Hashim, Kamaruddin

    2015-04-01

    Modification of nylon-6 fibres by radiation-induced graft copolymerisation (RIGP) of vinylbenzyl chloride (VBC) using the preirradiation method was investigated. A number of grafting parameters such as type of solvent, total dose, monomer concentrations, reaction temperature and reaction time were studied to obtain desired degree of grafting (DG). The DG was found to be a function of reaction parameters and achieved a maximum value of 130 wt% at 20 vol% VBC concentration in methanol, 300 kGy dose, 30 °C temperature and 3 h reaction time. Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to evaluate the chemical, morphological and structural changes that occurred in the grafted fibres, respectively. Thermogravimetric analysis (TGA) was also applied to determine the thermal stability, whereas differential scanning calorimeter (DSC) and universal mechanical tester were used to analyse respective thermal and mechanical properties of the grafted fibres. The results of these analyses provide strong evidence for successful grafting of VBC onto nylon-6, and the variation in the properties of the grafted fibres depends on DG.

  6. Radiation grafting of maleic anhydride onto polypropylene in solid state via ultrafine blend

    NASA Astrophysics Data System (ADS)

    Tan, Xiumin

    2014-05-01

    A novel method to prepare maleic anhydride grafting onto poly (propylene) (PP-g-MAH) was described. It was performed by γ-irradiation in solid state via ultrafine blend in the absence of any initiator and the grafting mechanism was proposed based on the experimental results. First, ultrafine blend of MAH and PP was prepared through ultrasonic initiation in melt state and then cooled rapidly. Second, the blend was radiated by γ-irradiation in the circumstance of atmosphere. Effects of irradiation dose and MAH concentration on the amount of grafted MAH were investigated. Compared with the conventional solid-state radiation grafting method, PP-g-MAH obtained via this method shows a higher graft rate of MAH. This novel method also has the advantages of solventless, energy efficient, low cost and simple operation. Furthermore, it is very easy to get purified products. The molecular structures of grafted copolymer were characterized by Fourier-transform infrared spectroscopy. Differential scanning calorimetry, wide-angle X-ray diffraction and polarized optical microscope were used to determine the degree of crystallinity and crystalline structure.

  7. Achieving highly effective non-biofouling performance for polypropylene membranes modified by UV-induced surface graft polymerization of two oppositely charged monomers.

    PubMed

    Zhao, Yong-Hong; Zhu, Xiao-Ying; Wee, Kin-Ho; Bai, Renbi

    2010-02-25

    A major problem in membrane technology for applications such as wastewater treatment or desalination is often the loss of membrane permeability due to biofouling initiated from protein adsorption and biofilm formation on the membrane surface. In this study, we developed a relatively simple and yet versatile approach to prepare polypropylene (PP) membrane with highly effective non-biofouling performance. Copolymer brushes were grafted to the surface of PP membrane through UV-induced polymerization of two oppositely charged monomers, i.e., [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TM) and 3-sulfopropyl methacrylate potassium salt (SA), with varying TM:SA molar ratios. Surface analysis with scanning electron microscope (SEM) clearly showed the grafted copolymer brushes on the membrane surfaces and that with X-ray photoelectron spectroscope (XPS) revealed a similar TM:SA ratio of the grafted copolymer brushes to that of the monomer solution used for the polymerization. Water contact angle measurements indicated that the hydrophilicity of the membrane surfaces was remarkably improved by the grafting of the TM/SA copolymer brushes, with the lowest water contact angle of 27 degrees being achieved at the TM:SA ratio of around 1:1. Experiments for antiprotein adsorption with bovine serum album (BSA) and lysozyme (LYZ) and antibiofilm formation with Escherichia coli (E. coli) demonstrated a great dependence of the membrane performance on the TM:SA ratios of the grafted copolymer brushes. It was found that the characteristics of the surface charges of the membrane surfaces played a very important role in the non-biofouling performance, and the membrane surface with balanced positive and negative charges showed the best non-biofouling performance for the proteins and bacteria tested in this study. PMID:20121056

  8. Radiation-grafting of thermo- and pH-responsive poly(N-vinylcaprolactam-co-acrylic acid) onto silicone rubber and polypropylene films for biomedical purposes

    NASA Astrophysics Data System (ADS)

    Ferraz, Caroline C.; Varca, Gustavo H. C.; Ruiz, Juan-Carlos; Lopes, Patricia S.; Mathor, Monica B.; Lugão, Ademar B.; Bucio, Emilio

    2014-04-01

    This work focuses on the effects of gamma-ray irradiation conditions on the stimuli-responsiveness of polypropylene (PP) films and silicone (SR) rubber substrates grafted with N-vinylcaprolactam (NVCL) and acrylic acid (AAc). PP films and SR rubber were modified by simultaneous polymerization and grafting of NVCL and AAc, using pre-irradiation oxidative method at a dose rate of 12.23 kGy h-1 and doses ranging from 5 to 70 kGy. NVCL and AAc solutions (1/1, v/v) at 50% monomer concentration (v/v) in toluene were added to the sample substrates, degassed, sealed and heated at 60 and 70 °C for 12 h. After grafting, the samples were soaked in ethanol and distilled water for 24 h successively, followed by drying under vacuum. Samples were characterized by FTIR-ATR, DSC and swelling measurements. Critical points (pH critical or LCST) of grafts were obtained in a pH-environment (pH ranges from 2.2 to 9) and in a thermo-environment (temperature ranges from 22 to 50 °C). Cytotoxicity evaluation was performed using fibroblast BALB/c 3T3 cells. The relationship between NVCL-co-AAc grafting and radiation dose was different for each substrate, PP and SR. At 50% NVCL/AAc concentration in toluene, grafting values were higher for SR than for PP. Despite the fact that PP-g-(NVCL-co-AAc) membrane presented a cytotoxic profile at the highest experimental concentration assayed, cytotoxicity evaluation revealed noncytotoxic profiles for the membranes synthesized highlighting their applications for biomedical purposes.

  9. Subacute radiation dermatitis: a histologic imitator of acute cutaneous graft-versus-host disease

    SciTech Connect

    LeBoit, P.E.

    1989-02-01

    The histopathologic changes of radiation dermatitis have been classified either as early effects (necrotic keratinocytes, fibrin thrombi, and hemorrhage) or as late effects (vacuolar changes at the dermal-epidermal junction, atypical radiation fibroblasts, and fibrosis). Two patients, one exposed to radiation therapeutically and one accidentally, are described. Skin biopsy specimens showed an interface dermatitis characterized by numerous dyskeratotic epidermal cells with lymphocytes in close apposition (satellite cell necrosis); that is, the epidermal changes were similar to those in acute graft-versus-host disease. Because recipients of bone marrow transplants frequently receive total body irradiation as part of their preparatory regimen, the ability of radiation to cause persistent epidermal changes similar to those in acute graft-versus-host disease could complicate the interpretation of posttransplant skin biopsy specimens.

  10. Comparing calvarial transport distraction with and without radiation and fat grafting.

    PubMed

    Yuhasz, Mikell M; Koch, Felix P; Kwiatkowski, Anna; Young, Calvin; Clune, James; Travieso, Rob; Wong, Kenneth; Van Houten, Joshua; Steinbacher, Derek M

    2014-10-01

    The purpose of this study is to: a) assess transport distraction to reconstruct cranial defects in radiated and non-radiated fields b) examine adipose grafting's effect on the bony regenerate and overlying wound, and c) elucidate sources of bone formation during transport distraction osteogenesis. Twenty-three male New Zealand white rabbits (3 months; 3.5 kg) were used, 10 non-irradiated and 13 irradiated (17 treatment, 6 control) with a one-time fraction of 35 Gy. A 16 × 16 mm defect was abutted by a 10 × 16 mm transport disc 5 weeks after irradiation, and 11 animals were fat grafted at the distraction site. Latency (1 day), distraction (1.5 mm/day), and consolidation (4 weeks) followed. Fluorochromes were injected subcutaneously and microCT, fluorescence, and histology assessed. In distracted animals without fat grafting, bone density measured 701.87 mgHA/ccm and 2271.95 mgHA/ccm in irradiated and non-irradiated animals. In distracted animals with fat grafting, bone density measured 703.23 mgHA/ccm and 2254.27 mgHA/ccm in irradiated and non-irradiated animals. Fluorescence revealed ossification emanating from the dura, periosteum, and transport segment with decreased formation in irradiated animals. Transport distraction is possible for cranial reconstruction in irradiated fields but short-term osseous fill is significantly diminished. Adipose grafting enhances wound healing in previously irradiated fields but does not enhance ossification. PMID:24864072

  11. [Evaluation of Radiation Dose during Stent-graft Treatment Using a Hybrid Operating Room System].

    PubMed

    Haga, Yoshihiro; Chida, Kouichi; Kaga, Yuji; Saitou, Kazuhisa; Arai, Takeshi; Suzuki, Shinichi; Iwaya, Yoshimi; Kumasaka, Eriko; Kataoka, Nozomi; Satou, Naoto; Abe, Mitsuya

    2015-12-01

    In recent years, aortic aneurysm treatment with stent graft grafting in the X-ray fluoroscopy is increasing. This is an endovascular therapy, because it is a treatment which includes the risk of radiation damage, having to deal with radiation damage, to know in advance is important. In this study, in order to grasp the trend of exposure stent graft implantation in a hybrid operating room (OR) system, focusing on clinical data (entrance skin dose and fluoroscopy time), was to count the total. In TEVAR and EVAR, fluoroscopy time became 13.40 ± 7.27 minutes, 23.67 ± 11.76 minutes, ESD became 0.87 ± 0.41 mGy, 1.11 ± 0.57 mGy. (fluoroscopy time of EVAR was 2.0 times than TEVAR. DAP of EVAR was 1.2 times than TEVAR.) When using the device, adapted lesions and usage are different. This means that care changes in exposure-related factors. In this study, exposure trends of the stent graft implantation was able to grasp. It can be a helpful way to reduce/optimize the radiation dose in a hybrid OR system. PMID:26685833

  12. Specialty polymeric membranes. 8: Separation of benzene from benzene/cyclohexane mixtures with nylon 6-graft-poly(butyl methacrylate) membranes

    SciTech Connect

    Yoshikawa, Masakazu; Tsubouchi, Keisuke; Kitao, Toshio

    1999-02-01

    A novel pervaporation membrane was prepared by radical graft polymerization of butyl methacrylate onto nylon 6. The permselectivity toward benzene was increased by the introduction of poly(butyl methacrylate) onto a nylon 6 membrane. From pervaporation and sorption experiments, it was shown that the introduction of poly(butyl methacrylate) onto a nylon 6 membrane leads to the enhancement of permselectivity toward benzene. The solubility data for benzene were described by a combination of simple sorption and specific sorption, while cyclohexane solubility was described by simple sorption.

  13. Synergistic effect on corrosion resistance of Phynox substrates grafted with surface-initiated ATRP (co)polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and 2-hydroxyethyl methacrylate (HEMA).

    PubMed

    Barthélémy, Bastien; Maheux, Simon; Devillers, Sébastien; Kanoufi, Frédéric; Combellas, Catherine; Delhalle, Joseph; Mekhalif, Zineb

    2014-07-01

    Phynox is of high interest for biomedical applications due to its biocompatibility and corrosion resistance. However, some Phynox applications require specific surface properties. These can be imparted with suitable surface functionalizations of its oxide layer. The present work investigates the surface-initiated atom transfer radical polymerization (ATRP) of 2-methacryloyoxyethyl phosphorylcholine (MPC), 2-hydroxyethyl methacrylate (HEMA), and ATRP copolymerization of (HEMA-co-MPC) (block and statistic copolymerization with different molar ratios) on grafted Phynox substrates modified with 11-(2-bromoisobutyrate)-undecyl-1-phosphonic acid (BUPA) as initiator. It is found that ATRP (co)polymerization of these monomers is feasible and forms hydrophilic layers, while improving the corrosion resistance of the system. PMID:24915233

  14. In-situ formation of silver nanoparticles on poly (lactic acid) film by γ-radiation induced grafting of N-vinyl pyrrolidone.

    PubMed

    Wang, Jingxia; Chen, Hao; Chen, Zhuping; Chen, Yuheng; Guo, Dan; Ni, Maojun; Liu, Siyang; Peng, Chaorong

    2016-06-01

    A fast, easy and novel method for preparing biodegradable polymer films with silver nanoparticles was investigated to endow the material with excellent biocompatibility and antibacterial property. Silver nanoparticles (Ag NPs) were immobilized on the surface of polylactic acid (PLA) film by gamma radiation induced grafting of N-vinyl pyrrolidone (NVP). In this method, poly (N-vinyl pyrrolidone) (PVP) was produced and grafted onto the surface of PLA film by gamma radiation polymerization of NVP. PVP acted as both a bridge to connect the Ag NPs with the PLA film, and a stabilizer to protect the Ag NPs from agglomeration. The effect of various reaction parameters, including NVP/Ag mole ratio and radiation dose, on the fabrication of PLA-g-NVP/Ag film was demonstrated. Moreover, the interaction between PVP and Ag NPs was studied by X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, that revealed the Ag NPs coordinated through the oxygen atom on the carbonyl group of PVP at 15kGy radiation dose, but through the nitrogen atom and the oxygen atom of the amide group of PVP at 1kGy dose. PMID:27040205

  15. Modification of fiber properties through grafting of acrylonitrile to rayon by chemical and radiation methods

    PubMed Central

    Kaur, Inderjeet; Sharma, Neelam; Kumari, Vandna

    2013-01-01

    Fibrous properties of rayon has been modified through synthesis of graft copolymers of rayon with acrylonitrile (AN) by chemical method using ceric ammonium nitrate (CAN/HNO3) as a redox initiator and gamma radiation mutual method. Percentage of grafting (Pg) was determined as a function of initiator concentration, monomer concentration, irradiation dose, temperature, time of reaction and the amount of water. Maximum percentage of grafting (160.01%) using CAN/HNO3 was obtained at [CAN] = 22.80 × 10−3 mol/L, [HNO3] = 112.68 × 10−2 mol/L and [AN] = 114.49 × 10−2 mol/L in 20 mL of water at 45 °C within 120 min while in case of gamma radiation method, maximum Pg (90.24%) was obtained at an optimum concentration of AN of 76.32 × 10−2 mol/L using 10 mL of water at room temperature with total dose exposure of 3.456 kGy/h. The grafted fiber was characterized by FTIR, SEM, TGA and XRD studies. Swelling behavior of grafted rayon in different solvents such as water, methanol, ethanol, DMF and acetone was studied and compared with the unmodified rayon. Dyeing behavior of the grafted fiber was also investigated. PMID:25685464

  16. Modification of fiber properties through grafting of acrylonitrile to rayon by chemical and radiation methods.

    PubMed

    Kaur, Inderjeet; Sharma, Neelam; Kumari, Vandna

    2013-11-01

    Fibrous properties of rayon has been modified through synthesis of graft copolymers of rayon with acrylonitrile (AN) by chemical method using ceric ammonium nitrate (CAN/HNO3) as a redox initiator and gamma radiation mutual method. Percentage of grafting (Pg) was determined as a function of initiator concentration, monomer concentration, irradiation dose, temperature, time of reaction and the amount of water. Maximum percentage of grafting (160.01%) using CAN/HNO3 was obtained at [CAN] = 22.80 × 10(-3) mol/L, [HNO3] = 112.68 × 10(-2) mol/L and [AN] = 114.49 × 10(-2) mol/L in 20 mL of water at 45 °C within 120 min while in case of gamma radiation method, maximum Pg (90.24%) was obtained at an optimum concentration of AN of 76.32 × 10(-2) mol/L using 10 mL of water at room temperature with total dose exposure of 3.456 kGy/h. The grafted fiber was characterized by FTIR, SEM, TGA and XRD studies. Swelling behavior of grafted rayon in different solvents such as water, methanol, ethanol, DMF and acetone was studied and compared with the unmodified rayon. Dyeing behavior of the grafted fiber was also investigated. PMID:25685464

  17. Radiation-induced graft copolymer SBS-g-VP for biomaterial usage.

    PubMed

    Yang, J M; Hsiue, G H

    1996-06-01

    The grafting of 4-vinyl pyridine (VP) to styrene-butadienestyrene triblock copolymer (SBS) by radiation-induced graft copolymerization was studied. The cohesive properties such as cohesive energy (Ecoh), molar volume (V), solubility parameter (delta), molar molecular weight (WM), specific volume (Vg), and density (1/Vg) of SBS-g-VP graft copolymer were calculated according to the group contribution of Fedors. The morphology of SBS-g-VP was studied by optical polarizing microscopy. We also measured the glass transition temperature and the mechanical properties of SBS-g-VP graft copolymer. Contact angle and blood-clotting time experiments were also performed to evaluate the biocompatibility of SBS-g-VP. A second domain was found in the SBS-g-VP graft copolymer, which resulted in different properties between SBS-g-VP and SBS. The blood compatibility of SBS-g-VP as measured by the Lee-White clotting test was better than that of SBS and polystyrene. PMID:8731218

  18. Influence of Space Radiation on the Outgassing Rate of a Patterned Polymeric Composite in Vacuum

    SciTech Connect

    Khasanshin, R. H.; Timofeev, A. N.; Ivanov, M. F.

    2009-01-05

    Experimental results on outgassing rates of patterned polymeric composites preliminary subjected to separate and combined radiation have been analyzed and presented. Mathematical models describing the outgassing processes in these materials were used for interpretation of the experimental data. Numerical results found using the models are presented.

  19. High performance radiation-grafted membranes and electrodes for polymer electrolyte fuel cells

    SciTech Connect

    Nezu, Shinji; Seko, Hideo; Gondo, Masaki; Ito, Naoki

    1996-12-31

    Polymer electrolyte fuel cells (PEFC) have attracted much attention for stationary and electric vehicle applications. Much progress has been made to improve their performance recently. However there are still several problems to overcome for commercialization. Among them, the cost of polymer electrolyte membranes seems to be rather critical, because a cost estimate of a practical fuel cell stack shows that the membrane cost must be reduced at least by two orders of magnitude based on current perfluorosulfonic acid membranes eg. Nafion{reg_sign}. Thus the development of new membrane materials is strongly desired. Styrene grafted tetrafluoroethylene-hexafluoropropylene copolymer (FEP) membranes have been studied for a fuel cell application by G. Scherer et al. These authors showed that membranes obtained by radiation grafting served as an alternative membrane for fuel cells although there were several problems to overcome in the future. These problems include shorter life time which was concluded to result from the decomposition of grafted polystyrene side chains. We report here the performance of our fuel cells which were fabricated from our radiation grafted membranes (IMRA MEMBRANE) and gas diffusion electrodes.

  20. Laser radiation in the treatment of prosthetic graft stenosis. A preliminary study of prosthesis damage by laser energy

    SciTech Connect

    Seeger, J.M.; Abela, G.S.; Klingman, N.

    1987-09-01

    Transluminal laser recanalization is potentially an important new treatment of anastomotic intimal hyperplasia. However, currently used grafts or sutures may be damaged by laser radiation at power and energy levels required for plaque removal. To investigate this problem, two commonly used grafts (Dacron and polytetrafluoroethylene (PTFE)) and two types of vascular suture (polypropylene and PTFE) were exposed to argon laser radiation in vitro. Dacron and PTFE grafts recovered from amputations were also studied to determine whether graft healing affected graft resistance to laser damage. Power and energy levels required to perforate atherosclerotic superficial femoral arteries were determined for comparison. PTFE grafts were significantly (1.5 to 7 times) more resistant to perforation by laser energy than atherosclerotic arteries under all conditions. In contrast, Dacron grafts perforated at power and energy levels one half to one third of that required for vaporization of atherosclerotic plaque. PTFE sutures remained intact at power and energy levels above the levels that perforated atherosclerotic arteries, whereas polypropylene sutures were destroyed by very low levels of power and energy (0.5 joules at 0.5 watts). Because of the variable levels of power and energy that damage different types of prosthetic grafts and sutures, laser angioplasty should only be investigated clinically as a therapy for anastomotic intimal hyperplasia when PTFE grafts and sutures are present.

  1. Synthesis and characterization of thermo- and pH- sensitive hydrogels based on Chitosan-grafted N-isopropylacrylamide via γ-radiation

    NASA Astrophysics Data System (ADS)

    Cai, Hong; Zhang, Zheng Pu; Chuan Sun, Ping; Lin He, Bing; Xia Zhu, Xiao

    2005-09-01

    Thermo- and pH-sensitive hydrogels were prepared by graft copolymerization of chitosan (CS) and N-isopropylacrylamide via γ-radiation. The effects of monomer concentration and irradiation dose on grafting percentage and grafting efficiency were studied. The graft copolymers were characterized by 13C CP/MAS NMR and thermogravimetric analysis. The pH and thermosensitivity and swelling properties of the hydrogels were investigated. The results showed that the grafting percentage and grafting efficiency increased with the increase of monomer concentration and total irradiation dose. The highest grafting percentage is 620%, the lower critical solution temperature (LCST) of this hydrogel is about 28 °C.

  2. Cellulose based cationic adsorbent fabricated via radiation grafting process for treatment of dyes waste water.

    PubMed

    Goel, Narender Kumar; Kumar, Virendra; Misra, Nilanjal; Varshney, Lalit

    2015-11-01

    A cationized adsorbent was prepared from cellulosic cotton fabric waste via a single step-green-radiation grafting process using gamma radiation source, wherein poly[2-(methacryloyloxy) ethyl]trimethylammonium chloride (PMAETC) was covalently attached to cotton cellulose substrate. Radiation grafted (PMAETC-g-cellulose) adsorbent was investigated for removal of acid dyes from aqueous solutions using two model dyes: Acid Blue 25 (AB25) and Acid Blue 74 (AB74). The equilibrium adsorption data was analyzed by Langmuir and Freundlich isotherms, whereas kinetic data was analyzed by pseudo first order, pseudo second order, intra particle diffusion and Boyd's models. The PMAETC-g-cellulose adsorbent with 25% grafting yield exhibited equilibrium adsorption capacities of ∼ 540.0mg/g and ∼ 340.0mg/g for AB25 and AB74, respectively. Linear and nonlinear fitting of adsorption data suggested that the equilibrium adsorption process followed Langmuir adsorption isotherm model, whereas, the kinetic adsorption process followed pseudo-second order model. The multi-linearities observed in the intra-particle kinetic plots suggested that the intraparticle diffusion was not the only rate-controlling process in the adsorption of acid dyes on the adsorbent, which was further supported by Boyd's model. The adsorbent could be regenerated by eluting the adsorbed dye from the adsorbent and could be repeatedly used. PMID:26256369

  3. Influence of matrix porosity on the immobilization of penicillin acylase by radiation-induced polymerization

    NASA Astrophysics Data System (ADS)

    Carenza, M.; Lora, S.; Palma, G.; Boccù, E.; Largajolli, R.; Veronese, F. M.

    Penicillin acylase was immobilized by low temperature radiation-induced polymerization into polymer matrices obtained from monomers of different hydrophilicities, at various ratios of monomer to enzyme solution and at different polymerization conversions. It was found that the penicillin acylase retention (60-85% of the starting enzyme) is independent of the monomer used in thepolymerization, of the polymerization conversion and of the porosity of the polymer matrix. On the other hand, the penicillin acylase retention strongly depends on the presence in the irradiation mixture of the hydrophobic crosslinking agent, trimethylolpropane trimethacrylate, even in low amounts. The data suggest that the enzyme is bound to the polymer matrix by hydrophobic interactions through crosslinking agent molecules.

  4. Ultraviolet/Ozone as a Tool To Control Grafting Density in Surface-Initiated Controlled-Radical Polymerizations via Ablation of Bromine.

    PubMed

    Sheridan, Richard J; Orski, Sara V; Muramoto, Shin; Stafford, Christopher M; Beers, Kathryn L

    2016-08-16

    We used an ultraviolet-ozone (UVO) cleaner to create substrates for atom-transfer radical polymerization (ATRP) with varying surface initiator coverage. We collected complementary time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) measurements to investigate the precise chemical origin of the variation in grafting density. At short exposure times, the atomic composition underwent minor changes except for the relative amount of bromine. At longer UVO exposure times, there is clear evidence of exposure-dependent surface initiator oxidation. We interpret these data as evidence of a bromine ablation process within the UVO cleaner, with additional oxidative modification of the rest of the surface. We then used these substrates to create a series of poly(methyl methacrylate) (PMMA) brushes varying in grafting density, demonstrating the utility of this tool for the control of polymer brush density. The measured brush grafting densities were correlated with the bromine concentration measured by both ToF-SIMS and XPS. XPS and brush thicknesses correlated strongly, following an exponential decay with a half-life of 18 ± 1 s. PMID:27442615

  5. Modification of flax fibres by radiation induced emulsion graft copolymerization of glycidyl methacrylate

    NASA Astrophysics Data System (ADS)

    Moawia, Rihab Musaad; Nasef, Mohamed Mahmoud; Mohamed, Nor Hasimah; Ripin, Adnan

    2016-05-01

    Flax fibres were modified by radiation induced graft copolymerization of glycidyl methacrylate (GMA) by pre-irradiation method in an emulsion medium. The effect of reaction parameters on the degree of grafting (DOG) such as concentration of bleaching agent, absorbed dose, monomer concentration, temperature and reaction time were investigated. The DOG was found to be dependent on the investigated parameters. The incorporation of poly(GMA) grafts in the bleached flax fibres was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The structural and mechanical changes were evaluated by X-ray diffraction (XRD) and mechanical tester, respectively. The results revealed that reacting bleached flax fibres irradiated with 20 kGy with 5% GMA emulsion containing 0.5% polyoxyethylene-sorbitan monolaurate (Tween 20) surfactant at 40 °C for 1 h led to a maximum DOG of 148%. The grafted fibres showed sufficient mechanical strength and hydrophobicity which make them promising precursors for development of adsorbents after appropriate chemical treatments.

  6. Preparation and characterization of a magneto-polymeric nanocomposite: Fe 3O 4 nanoparticles in a grafted, cross-linked and plasticized poly(vinyl chloride) matrix

    NASA Astrophysics Data System (ADS)

    Rodríguez-Fernández, Oliverio S.; Rodríguez-Calzadíaz, C. A.; Yáñez-Flores, Isaura G.; Montemayor, Sagrario M.

    In this work two kind of materials: (1) grafted, cross-linked and plasticized poly(vinyl chloride) (PVC) "plastic films" and (2) magnetic plastic films "magneto-polymeric nanocomposites" were prepared. Precursor solutions or "plastisols" used to obtain the plastic films were obtained by mixing PVC (emulsion grade) as polymeric matrix, di(2-ethylhexyl)phthalate (DOP) as plasticizer, a thermal stabilizer based in Ca/Zn salts, and a cross-linking agent, 3-mercaptopropyltrimethoxysilane (MTMS) or 3-aminopropyltriethoxysilane (ATES), at several concentrations. Flexible films were obtained from the plastisols using static casting. The stress-strain behavior and the gel content (determined by Soxhlet extraction with boiling THF) of the flexible films were measured in order to evaluate the effect of the cross-linking agent and their content on the degree of cross-linking. The magneto-polymeric nanocomposites were obtained by mixing the optimum composition of the plastisols (analyzed previously) with magnetite (Fe 3O 4)-based ferrofluid and DOP. Later, flexible films were obtained by static casting of the plastisol/ferrofluid systems. The magnetic films were characterized by the above-mentioned techniques and X-ray diffraction, vibrating sample magnetometry and thermogravimetrical analysis.

  7. Comparative study of grafting a polyampholyte in a fluoropolymer membrane by gamma radiation in one or two-steps

    NASA Astrophysics Data System (ADS)

    Estrada-Villegas, G. M.; Bucio, E.

    2013-11-01

    Binary graft copolymerization of pH-sensitive monomers (N,N-dimethylaminoethyl methacrylate, (DMAEMA) and acrylic acid (AAc) onto polyvinylidene fluoride (PVDF) membranes with pore sizes of 0.22 and 0.45 μm was conducted by one and two-steps grafting using a 60Co gamma radiation source (Gammabeam 651 PT). The DMAEMA and AAc monomers were grafted by an oxidative pre-irradiation method in one-step grafting to obtain PDVF-g-(DMAEMA-co-AAc), and both direct irradiation and an oxidative pre-irradiation method were used to obtain the graft copolymer (PVDF-g-DMAEMA)-g-AAc in two-steps grafting. The optimal conditions, such as reaction time, temperature, solvent, monomer concentration and dose, were studied, the aim of this work was to investigate how these factors affecting the graft percent of DMAEMA and AAc prepared in one and two-steps grafting and their structural differences and also characterize the grafting membrane through analytical techniques.

  8. Radiation grafted and sulfonated (FEP-g-polysterene) - An alternative to perfluorinated membranes for PEM fuel cells?

    NASA Astrophysics Data System (ADS)

    Buechi, F. N.; Gupta, B.; Rouilly, M.; Hauser, P. C.; Chapiro, A.; Scherer, G. G.

    Partially fluorinated proton exchange membranes (PEMs) were synthesized for fuel cell applications by simultaneous radiation grafting of styrene on FEP films followed by sulfonation. Properties of the synthesized membranes can be tailored by varying the degree of grafting and crosslinking. The performance of these membranes was tested in H2/O2 fuel cells. Long time testing showed steady performance for high grafted membranes over periods of more than 300 h at a cell temperature of 60 C. Low grafted membranes and the Morgane CDS membrane showed considerable decay of cell power on the same time scale. A fast degradation of all membranes occurred at a cell temperature of 80 C. It is noted that grafting in film form makes this process a potentially cheap and easy technique for the preparation of solid polymer fuel cell electrolytes.

  9. Fundamental investigation of ultraviolet radiation effects in polymeric film-forming materials

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.; Llewellen, P.; Gilligan, J.

    1974-01-01

    A literature search from 1958 to present was conducted on the effect of ultraviolet radiation on polymeric materials, with particular emphasis on vacuum photolysis, mechanisms of degradation, and energy transfer phenomena. The literature from 1958 to 1968 was searched manually, while the literature from 1968 to present was searched by using a computerized keyword system. The primary objective was to provide the necessary background information for the design of new or modified materials with improved stability to the vacuum-radiation environment of space.

  10. Radiation induced graft copolymerization of n-butyl acrylate onto poly(ethylene terephthalate) (PET) films and thermal properties of the obtained graft copolymer

    NASA Astrophysics Data System (ADS)

    Ping, Xiang; Wang, Mozhen; Ge, Xuewu

    2011-05-01

    n-Butyl acrylate (BA) was successfully grafted onto poly(ethylene terephthalate) (PET) film using simultaneous radiation induced graft copolymerization with gamma rays. When BA concentration ranges from 20% to 30%, the Degree of Grafting (DG), measured by gravimetry and 1H NMR, increases with the monomer concentration and absorbed dose, but decreases with dose rate from 0.83 to 2.53 kGy/h. The maximum DG can reach up to 22.1%. The thermal transition temperatures such as glass-transition temperature ( Tg) and cold-crystallization temperature ( Tcc) of PET in grafted films were little different from those in original PET film, indicating that microphase separation occurred between PBA side chains and PET backbone. This work implied that if PET/elastomers (e.g., acrylate rubber) blends are radiated by high energy gamma rays under a certain condition, PET-g-polyacrylate copolymer may be produced in-situ, which will improve the compatibility between PET and the elastomers so as to improve the integral mechanical properties of PET based engineering plastic.

  11. Analysis of Mass Loss of a Polymeric Composite under Space Radiations

    NASA Astrophysics Data System (ADS)

    Khasanshin, Rashid

    2016-07-01

    Polymeric materials find ever-widening application in space technique. This is tied with the simplicity of producing the polymeric-based composites with the predetermined set of properties. However, these materials in space become the sources of volatile products that increase density of spacecraft outer atmosphere that undermines on serviceability of the on-board equipment. Therefore, study of mass loss of spacecraft materials in service conditions is a vital task. Polymeric composites are often used as thermal control coatings (TCC), which are subjected to maximum radiation exposure in service. It is known that irradiation of a PC is accompanied by intense gas formation but evolution of volatile products (VP) through the material-vacuum surface is limited by diffusion. Well-developed surface together with little thickness of a TCC film facilitate migration of radiolysis products to free coating surface. In this case outgassing and destruction of material augment permeability of the film, accelerate migration processes and make them easier. This work is devoted to studying action of separate (electron, proton, and electromagnetic), paired, and the whole set of radiations on mass loss of a pattern material in vacuum. The primary focus was on studying and interpretation of synergistic effects appearing in the course of mass loss of the pattern materials EKOM-1 and EKOM-2 polymeric composites, the widely used spacecraft TCC. Irradiation was made by 20-50-keV electrons and 20-keV protons and electromagnetic radiation in vacuum chamber of the UV-1/2 test facility. It was found that parameters characterizing the synergistic effects of mass loss of the material for fixed conditions of electron-proton and combined radiations are the functions of irradiation time. To interpret the experimental data, a physical-mathematical model of mass loss of polymeric materials in vacuum was proposed. The obtained data can be explained by diffusion fluxes associated with the gradient of

  12. Highly hydrophilic ultra-high molecular weight polyethylene powder and film prepared by radiation grafting of acrylic acid

    NASA Astrophysics Data System (ADS)

    Wang, Honglong.; Xu, Lu.; Li, Rong.; Pang, Lijuan.; Hu, Jiangtao.; Wang, Mouhua.; Wu, Guozhong.

    2016-09-01

    The surface properties of ultra-high molecular weight polyethylene (UHMWPE) are very important for its use in engineering or composites. In this work, hydrophilic UHMWPE powder and film were prepared by γ-ray pre-irradiation grafting of acrylic acid (AA) and further neutralization with sodium hydroxide solution. Variations in the chemical structure, grafting yield and hydrophilicity were investigated and compared. FT-IR and XPS analysis results showed that AA was successfully grafted onto UHMWPE powder and film; the powder was more suitable for the grafting reaction in 1 wt% AA solution than the film. Given a dose of 300 kGy, the grafting yield of AA was ∼5.7% for the powder but ∼0.8% for the film under identical conditions. Radiation grafting of a small amount of AA significantly improved the hydrophilicity of UHMWPE. The water contact angle of the UHMWPE-g-PAA powder with a grafting yield of AA at ∼5.7% decreased from 110.2° to 68.2°. Moreover, the grafting powder (UHMWPE-g-PAA) exhibited good dispersion ability in water.

  13. Poly(2-hydroxyethyl methacrylate) grafted halloysite nanotubes as a molecular host matrix for luminescent ions prepared by surface-initiated RAFT polymerization and coordination chemistry

    NASA Astrophysics Data System (ADS)

    Islam, Md. Rafiqul; Bach, Long Giang; Lim, Kwon Taek

    2013-07-01

    A fluorescent nanohybrid complex comprising of halloysite nanotubes (HNTs), poly(2-hydroxyethyl methacrylate) (PHEMA), and europium ions (Eu3+) was synthesized by the combination of surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization and coordination chemistry. Initially, PHEMA was grafted from the HNTs by SI-RAFT and then reacted with succinic anhydride to provide carboxyl acid groups on the external layers of HNTs-g-PHEMA nanohybrids. The subsequent coordination of the nanohybrids with Eu3+ ions afforded photoluminescent Eu3+ tagged HNTs-g-PHEMA nanohybrid complexes (HNTs-g-PHEMA-Eu3+). The structure, morphology, and fluorescence properties of the Eu3+ coordinated nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR, XPS, and EDS analyses suggested the formation of the HNTs-g-PHEMA-Eu3+ nanohybrids. FE-SEM images indicated the immobilization of polymer layers on HNTs. TGA scans further demonstrated the grafting of PHEMA onto HNTs surface. The optical properties of HNTs-g-PHEMA-Eu3+ nanohybrid complexes were investigated by photoluminescence spectroscopy.

  14. Grafting of poly[(methyl methacrylate)-block-styrene] onto cellulose via nitroxide-mediated polymerization, and its polymer/clay nanocomposite.

    PubMed

    Karaj-Abad, Saber Ghasemi; Abbasian, Mojtaba; Jaymand, Mehdi

    2016-11-01

    For the first time, nitroxide-mediated polymerization (NMP) was used for synthesis of graft and block copolymers using cellulose (Cell) as a backbone, and polystyrene (PSt) and poly(methyl metacrylate) (PMMA) as the branches. For this purpose, Cell was acetylated by 2-bromoisobutyryl bromide (BrBiB), and then the bromine group was converted to 4-oxy-2,2,6,6-tetramethylpiperidin-1-oxyl group by a substitution nucleophilic reaction to afford a macroinitiator (Cell-TEMPOL). The macroinitiator obtained was subsequently used in controlled graft and block copolymerizations of St and MMA monomers to yield Cell-g-PSt and Cell-g-(PMMA-b-PSt). The chemical structures of all samples as representatives were characterized by FTIR and (1)H NMR spectroscopies. In addition, Cell-g-(PMMA-b-PSt)/organophilic montmorillonite nanocomposite was prepared through a solution intercalation method. TEM was used to evaluate the morphological behavior of the polymer-clay system. It was demonstrated that the addition of small percent of organophilic montmorillonite (O-MMT; 3wt.%) was enough to improve the thermal stability of the nanocomposite. PMID:27516276

  15. Grafting of Poly(methyl methacrylate) Brushes from Magnetite Nanoparticles Using a Phosphonic Acid Based Initiator by Ambient Temperature Atom Transfer Radical Polymerization (ATATRP)

    PubMed Central

    2008-01-01

    Poly(methyl methacrylate) in the brush form is grown from the surface of magnetite nanoparticles by ambient temperature atom transfer radical polymerization (ATATRP) using a phosphonic acid based initiator. The surface initiator was prepared by the reaction of ethylene glycol with 2-bromoisobutyrl bromide, followed by the reaction with phosphorus oxychloride and hydrolysis. This initiator is anchored to magnetite nanoparticles via physisorption. The ATATRP of methyl methacrylate was carried out in the presence of CuBr/PMDETA complex, without a sacrificial initiator, and the grafting density is found to be as high as 0.90 molecules/nm2. The organic–inorganic hybrid material thus prepared shows exceptional stability in organic solvents unlike unfunctionalized magnetite nanoparticles which tend to flocculate. The polymer brushes of various number average molecular weights were prepared and the molecular weight was determined using size exclusion chromatography, after degrafting the polymer from the magnetite core. Thermogravimetric analysis, X-ray photoelectron spectra and diffused reflection FT-IR were used to confirm the grafting reaction.

  16. Role of Polymeric Endosomolytic Agents in Gene Transfection: A Comparative Study of Poly(l-lysine) Grafted with Monomeric l-Histidine Analogue and Poly(l-histidine)

    PubMed Central

    2015-01-01

    Endosomal entrapment is one of the main barriers that must be overcome for efficient gene expression along with cell internalization, DNA release, and nuclear import. Introducing pH-sensitive ionizable groups into the polycationic polymers to increase gene transfer efficiency has proven to be a useful method; however, a comparative study of introducing equal numbers of ionizable groups in both polymer and monomer forms, has not been reported. In this study, we prepared two types of histidine-grafted poly(l-lysine) (PLL), a stacking form of poly(l-histidine) (PLL-g-PHis) and a mono- l-histidine (PLL-g-mHis) with the same number of imidazole groups. These two types of histidine-grafted PLL, PLL-g-PHis and PLL-g-mHis, showed profound differences in hemolytic activity, cellular uptake, internalization, and transfection efficiency. Cy3-labeled PLL-g-PHis showed strong fluorescence in the nucleus after internalization, and high hemolytic activity upon pH changes was also observed from PLL-g-PHis. The arrangement of imidazole groups from PHis also provided higher gene expression than mHis due to its ability to escape the endosome. mHis or PHis grafting reduced the cytotoxicity of PLL and changed the rate of cellular uptake by changing the quantity of free ε-amines available for gene condensation. The subcellular localization of PLL-g-PHis/pDNA measured by YOYO1-pDNA intensity was highest inside the nucleus, while the lysotracker, which stains the acidic compartments was lowest among these polymers. Thus, the polymeric histidine arrangement demonstrate the ability to escape the endosome and trigger rapid release of polyplexes into the cytosol, resulting in a greater amount of pDNA available for translocation to the nucleus and enhanced gene expression. PMID:25144273

  17. Radiation-induced cationic polymerization of limonene oxide,. cap alpha. -pinene oxide, and. beta. -pinene oxide

    SciTech Connect

    Aikins, J.A.; Williams, F.

    1984-01-01

    After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weight. A cationic mechanism is evidenced by the strongly retarding effect of tri-n-propylamine on the polymerization rate. At 25/sup 0/C, limonene oxide gives the highest polymerization rates, an average conversion of 36% per Mrad being obtained in comparison with values of 5.7 and 7.3% per Mrad for the ..cap alpha..-pinene and ..beta..-pinene oxides, respectively. Similarly, the average anti DP/sub n/ decreases from 11.8 for the limonene oxide polymer to 5.6 and 4.0 for the ..cap alpha..-pinene oxide and ..beta..-pinene oxide polymers, respectively. A high frequency of chain transfer to monomer is indicated in each case by the fact that the kinetic chain lengths are estimated to be on the order of a hundred times larger than the anti DP/sub n/ values. Structural characterization of the limonene oxide polymer by /sup 1/H and /sup 13/C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the ..cap alpha..-pinene and ..beta..-pinene oxides show that in the polymerization of these monomers, the opening of the epoxide ring is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-dimethyl group in the main chain. The detection of isopropenyl end groups in the pinene oxide polymers is also consistent with this mode of propagation being followed by chain (proton) transfer to monomer.

  18. Cell culture on polymers prepared by radiation-induced polymerization of various glass-forming monomers.

    PubMed

    Yoshii, F; Kaetsu, I

    1983-04-01

    The growth of cells on polymers prepared by the radiation polymerization of monomethacrylate and dimethacrylate was investigated. Cell growth was affected greatly by such properties of the polymers as water content, wettability, and porosity. Growth was promoted remarkably by rinsing the polymers with warm water at 60-70 degrees C and by irradiation of polymers with an electron beam. Cell growth decreased with increasing oxyethylene length (n) in the polymerized dimethacrylate of same series, CH2C(CH3)CO(OCH2CH2)nOCOC(CH3)CH2. A decrease in the hydrophilicity of the polymer increased cell growth rate. Formation of pore structures in the polymer films also increased the cell growth. PMID:6679189

  19. New Advanced Fabrication Technique for Millimeter-Wave Planar Components based on Fluororesin Substrates using Graft Polymerization

    NASA Astrophysics Data System (ADS)

    Ito, Naoki; Mase, Atsushi; Kogi, Yuichiro; Seko, Noriaki; Tamada, Masao; Sakata, Eiji

    2008-06-01

    As the importance of advanced millimeter-wave diagnostics increases, a reliable and accurate fabrication technique for high-performance devices and relevant components is essential. We describe a new improved fabrication technique for millimeter-wave planar components, such as antennas using low-loss fluororesin substrates. A fragile adhesion between the copper foil and fluororesin substrate and the accuracy of the device pattern using conventional fabrication techniques have been prime suspects in the failure of the devices. In order to solve these problems, surface treatment of fluororesin films and a fabrication method using electro-fine-forming (EF2) are proposed. The peel adhesion strength between the metal and fluororesin films and the value of the dielectric constant of the fluororesin films before and after grafting are reported. A prototype antenna using conventional fluororesin substrates and grafted-poly(tetrafluoroethylene) (PTFE) films produced using the EF2 fabrication technique are also introduced.

  20. Fractional epidermal grafting in combination with laser therapy as a novel approach in treating radiation dermatitis.

    PubMed

    Tran, Thanh-Nga Trinh; Hoang, Minh Van; Phan, Quynh-Anh Ngoc; Phung, Thuy L; Purschke, Martin; Ferinelli, William A; Sabir, Sameer; Ziegler, Andrew; Nelson, Stuart; Anderson, R Rox

    2015-03-01

    Radiation injury to the skin is a major source of dysfunction, disfigurement, and complications for thousands of patients undergoing adjunctive treatment for internal cancers. Despite the great potential for affecting quality of life, radiation injury has received little attention from dermatologists and is primarily being managed by radiation oncologists. During our volunteer work in Vietnam, we encountered numerous children with significant scarring and depigmentation of skin from the outdated use of radioactive phosphorus P32 in the treatment of hemangiomas. This dangerous practice has left thousands of children with significant fibrosis and disfigurement. Currently, there is no treatment for radiation dermatitis. Here, we report a case series using the combination of laser treatment, including pulsed-dye laser, fractional CO2 laser, and epidermal grafting to improve the appearance and function of the radiation scars in these young patients. We hope that by improving the appearance and function of these scars, we can improve the quality of life for these young patients and potentially open up a new avenue of treatment for cancer patients affected with chronic radiation dermatitis, potentially improving their range of motion, cosmesis, and reducing their risk of secondary skin malignancies. PMID:25922957

  1. Study of mass loss of spacecraft polymeric thermal control coatings under electron and proton radiations

    NASA Astrophysics Data System (ADS)

    Khasanshin, Rashid; Novikov, Lev; Galygin, Alexander

    Polymeric composites have a number of properties that give a possibility to apply them as spacecraft external coatings. In space environment, however, such materials become one of the main sources of volatile products that form the outer spacecraft atmosphere and are able to con-dense on contamination-sensitive surfaces of onboard equipment. Thermal control coatings oc-cupy a considerable part of a satellite surface and are mostly subjected to ionizing radiations ac-companying by outgassing. The main stages of the process are the following: formation of vola-tile radiolysis products, diffusion of the products to free material surface, and desorption. Radia-tion-induced destruction and outgassing of material increase its permeability and accelerate mi-gration processes in it. Experimental data of effect of radiation on mass loss of polymeric composites used as thermal control coatings was analyzed and interpreted in the work. As a particular case, it was shown that mass loss of a polymeric composite irradiated by protons is greater than by electrons if energies and flux densities of the particles are the same. It can be explained that volatile products, in the first case, generate within a thin near-surface layer of material which permeability increases together with the absorbed dose, and quickly escape in vacuum. In the second case, a bulk of volatile products emerges far enough from the free surface of material which permeability increases slower as compared with proton radiation. Therefore, migration time of volatile products to the free surface grows and quantity of chemical reactions which they are involved in increases. To analyze and interpret experimental data, a mathematical model describing mass loss of polymeric composites subject to its growth of permeability under radiation is proposed. Based upon analysis of experiments and numerical simulation results, thresholds of fluen-cies and flux densities of electron and proton were determined. Exceeding these

  2. Characterization and fuel cell testing of radiation-grafted PSI membranes

    SciTech Connect

    Brack, H.P.; Koebel, M.M.; Tsukada, A.; Huslage, J.; Buechi, F.; Geiger, F.; Rota, M.; Scherer, G.G.

    2000-07-01

    The authors have demonstrated earlier the useful performance of PSI radiation-grafted membranes in terms of the current-voltage characteristics of 30 cm{sup 2} active area fuel cells containing these membranes and their long-term testing over 6,000 h at 60 C. They report here on testing of PSI radiation-grafted membranes in these fuel cells at 80 C and in short stacks comprised of two or four 100 cm{sup 2} active area cells. The in-situ degradation of membranes has been investigated by characterizing membranes both before testing in fuel cells and post-mortem after testing in fuel cells. Characterization was accomplished by means of ion-exchange capacity and infrared and Raman spectroscopic measurements. In addition, a rapid screening method for ex-situ testing of the oxidative stability of proton-conducting membranes was developed in this work. Comparison of the initial screening test results concerning the oxidative stability of some perfluorinated, partially-fluorinated, and non-fluorinated membranes compare well qualitatively with the relative stability of these same membranes during their long-term testing in fuel cells.

  3. Radiation Protection Effectiveness of Polymeric Based Shielding Materials at Low Earth Orbit

    NASA Technical Reports Server (NTRS)

    Badavi, Francis F.; Stewart-Sloan, Charlotte R.; Wilson, John W.; Adams, Daniel O.

    2008-01-01

    Correlations of limited ionizing radiation measurements onboard the Space Transportation System (STS; shuttle) and the International Space Station (ISS) with numerical simulations of charged particle transport through spacecraft structure have indicated that usage of hydrogen rich polymeric materials improves the radiation shielding performance of space structures as compared to the traditionally used aluminum alloys. We discuss herein the radiation shielding correlations between measurements on board STS-81 (Atlantis, 1997) using four polyethylene (PE) spheres of varying radii, and STS-89 (Endeavour, 1998) using aluminum alloy spheres; with numerical simulations of charged particle transport using the Langley Research Center (LaRC)-developed High charge (Z) and Energy TRaNsport (HZETRN) algorithm. In the simulations, the Galactic Cosmic Ray (GCR) component of the ionizing radiation environment at Low Earth Orbit (LEO) covering ions in the 1< or equals Z< or equals 28 range is represented by O'Neill's (2004) model. To compute the transmission coefficient for GCR ions at LEO, O'Neill's model is coupled with the angular dependent LaRC cutoff model. The trapped protons/electrons component of LEO environment is represented by a LaRC-developed time dependent procedure which couples the AP8min/AP8max, Deep River Neutron Monitor (DRNM) and F10.7 solar radio frequency measurements. The albedo neutron environment resulting from interaction of GCR ions with upper atmosphere is modeled through extrapolation of the Atmospheric Ionizing Radiation (AIR) measurements. With the validity of numerical simulations through correlation with PE and aluminum spheres measurements established, we further present results from the expansion of the simulations through the selection of high hydrogen content commercially available polymeric constituents such as PE foam core and Spectra fiber(Registered TradeMark) composite face sheet to assess their radiation shield properties as compared to

  4. Uranium sorption by Pseudomonas biomass immobilized in radiation polymerized polyacrylamide bio-beads.

    PubMed

    D'Souza, S F; Sar, Pinaki; Kazy, Sufia K; Kubal, B S

    2006-01-01

    A Pseudomonas strain identified as a potent biosorbent of uranium (U) and thorium was immobilized in radiation-induced polyacrylamide matrix for its application in radionuclide containing wastewater treatment. The immobilized biomass exhibited a high U sorption of 202 mg g(-1) dry wt. with its optimum at pH 5.0. A good fit of experimental data to the Freundlich model suggested multilayered uranium binding with an affinity distribution among biomass metal binding sites. Scanning electron microscopy revealed a highly porous nature of the radiation-polymerized beads with bacterial cells mostly entrapped on pore walls. Energy dispersive X-ray analysis (EDXA) coupled with SEM ascertained the accumulation of uranium by the immobilized biomass without any physical damage to the cells. A significant (90%) part of biosorbed uranium was recovered using sodium bicarbonate with the immobilized biomass maintaining their U resorption capacity for multiple sorption-desorption cycles. Uranium loading and elution behavior of immobilized biomass evaluated within a continuous up-flow packed bed columnar reactor showed its effectiveness in removing uranium from low concentration (50 mg U L(-1)) followed by its recovery resulting in a 4-5-fold waste volume reduction. The data suggested the suitability of radiation polymerization in obtaining bacterial beads for metal removal and also the potential of Pseudomonas biomass in treatment of radionuclide containing waste streams. PMID:16484078

  5. Ionic polymer-metal composite actuators obtained from radiation-grafted cation- and anion-exchange membranes.

    PubMed

    Park, Jong Hyuk; Han, Man Jae; Song, Dae Seock; Jho, Jae Young

    2014-12-24

    Two series of ionic polymer-metal composites (IPMCs), one cationic and one anionic, are designed and prepared from radiation-grafted ion-exchange membranes. Through examination of the properties of the membranes synthesized from the two grafting monomers and the two base polymers, acrylic acid-grafted poly(vinylidene fluoride-co-hexafluoropropylene) and quarternized 4-vinylpyridine-grafted poly(ethylene-co-tetrafluoroethylene) with the appropriate amount of ionic groups are employed for the fabrication of cation and anion IPMCs, respectively. The bending displacement of the cation IPMC is comparable to Nafion-based IPMC under direct- and alternating-current voltage, but back-relaxation is not observed. The actuation performance of the anion IPMC is highly improved over those reported earlier in the literature for the other anion IPMCs. PMID:25420910

  6. Immobilization of yeast cells on hydrogel carriers obtained by radiation-induced polymerization

    NASA Astrophysics Data System (ADS)

    Xin, Lu Zhao; Carenza, Mario; Kaetsu, Isao; Kumakura, Minoru; Yoshida, Masaru; Fujimura, Takashi

    Polymer hydrogels were obtained by radiation-induced copolymerization at -78°C of aqueous solutions of acrylic and methacrylic esters. The matrices were characterized by equilibrium water content measurements, by optical microscopy observations and by scanning electron microscopy analysis. Yeast cells were immobilized on these hydrogels and the ethanol productivity by batch fermentation was determined. Matrix hydrophilicity and porosity were found to deeply influence the adhesion of yeast cells and, hence, the ethanol productivity. The latter as well as other physico-chemical properties were also affected by the presence of a crosslinking agent added in small amounts to the polymerizing mixture.

  7. Stability and Degradation Mechanisms of Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis.

    PubMed

    Albert, Albert; Lochner, Tim; Schmidt, Thomas J; Gubler, L

    2016-06-22

    Radiation-grafted membranes are a promising alternative to commercial membranes for water electrolyzers, since they exhibit lower hydrogen crossover and area resistance, better mechanical properties, and are of potentially lower cost than perfluoroalkylsulfonic acid membranes, such as Nafion. Stability is an important factor in view of the expected lifetime of 40 000 h or more of an electrolyzer. In this study, combinations of styrene (St), α-methylstyrene (AMS), acrylonitrile (AN), and 1,3-diisopropenylbenzene (DiPB) are cografted into 50 μm preirradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) base film, followed by sulfonation to produce radiation-grafted membranes. The stability of the membranes with different monomer combinations is compared under an accelerated stress test (AST), and the degradation mechanisms are investigated. To mimic the conditions in an electrolyzer, in which the membrane is always in contact with liquid water at elevated temperature, the membranes are immersed in water for 5 days at 90 °C, so-called thermal stress test (TST). In addition to testing in air atmosphere tests are also carried out under argon to investigate the effect of the absence of oxygen. The water is analyzed with UV-vis spectroscopy and ion chromatography. The ion exchange capacity (IEC), swelling degree, and Fourier transform infrared (FTIR) spectra of the membranes are compared before and after the test. Furthermore, energy-dispersive X-ray (EDX) spectroscopic analysis of the membrane cross-section is performed. Finally, the influence of the TST to the membrane area resistance and hydrogen crossover is measured. The stability increases along the sequence St/AN, St/AN/DiPB, AMS/AN, and AMS/AN/DiPB grafted membrane. The degradation at the weak-link, oxygen-induced degradation, and hydrothermal degradation are proposed in addition to the "swelling-induced detachment" reported in the literature. By mitigating the possible paths of degradation, the AMS

  8. PDMS-Glass bonding using grafted polymeric adhesive - Alternative process flow for compatibility with patterned biological molecules

    PubMed Central

    Beh, Cyrus Weijie; Zhou, Weizhuang

    2013-01-01

    We report a novel modification of silicone elastomer, polydimethylsiloxane (PDMS) with a polymer graft that allows interfacial bonding between elastomer and glass substrate to be performed without exposure of said substrate to harsh treatment conditions like oxygen plasma. Organic molecules can thus be patterned within microfluidic channels and still remain functional post-bonding. In addition, after polymer grafting the PDMS can be stored in a desiccator for at least 40 days, and activated upon exposure to acidic buffer for bonding. The bonded devices remain fully bonded in excess of 80 psi driving pressure, with no signs of compromise to the bond integrity. Finally, we demonstrate the compatibility of our method with biological molecules using a proof-of-concept DNA sensing device, in which fluorescently-labelled DNA targets are successfully captured by a patterned probe in a device sealed using our method, while the pattern on a plasma-treated device was completely destroyed. Therefore, this method provides a much-needed alternative bonding process for incorporation of biological molecules in microfluidic devices. PMID:22858861

  9. Synthesis of poly(N-isopropylacrylamide) hydrogels by radiation polymerization and cross-linking

    SciTech Connect

    Nagaoka, Noriyasu; Kubota, Hitoshi; Katakai, Ryoichi; Safranj, Agneza; Yoshida, Masaru; Omichi, Hideki

    1993-12-20

    Poly(N-isopropylacrylamide) [poly(NIPAAm)] shows a typical thermal reversibility of phase transition in aqueous solutions. That is, it precipitates from solution above a critical temperature called the lower critical solution temperature (LCST) and dissolves below this temperature. When it is cross-linked, the obtained hydrogel collapses above LCST, while it swells and expands below LCST. This hydrogel has received much attention recently and has been used as a model system to demonstrate the validity of theories describing the coil-globule transition, swelling of networks, and folding and unfolding of biopolymers. It has also been proposed for various applications ranging from controlled drug delivery to solute separation. Poly(NIPAAm) hydrogel is usually synthesized at room temperature from an aqueous solution of the monomer by using a redox initiator composed of ammonium persulfate and N,N,N{prime},N{prime}-tetramethylethylenediamine in the presence of N,N{prime}-methylenebisacrylamide as a cross-linker. Since the LCST of poly(NIPAAm) is around 32 C, the polymerization at room temperature proceeds in a homogeneous solution. Recently, poly(NIPAAm) hydrogels were synthesized by starting the polymerization below the LCST and then elevating the temperature above it, by which method macroporous gels with fast temperature response were obtained. The idea is to apply a radiation--induced polymerization method for the synthesis of poly(NIPAAm) hydrogels. This method offers unique advantages for synthesis: it is a simple and additive-free process at all temperatures, and the degree of cross-linking can be easily controlled by irradiation conditions. Therefore, radiation methods are especially attractive for the synthesis of hydrogels with potential biomedical application where the residual chemical initiators may contaminate the product. It is possible to combine into one step the synthesis and sterilization of the product, and it is economically competitive.

  10. Application of living radical polymerization to the synthesis of resist polymers for radiation lithography

    NASA Astrophysics Data System (ADS)

    Shimizu, Takashi; Ichikawa, Tsuneki

    2005-07-01

    Poly(styrene) and poly(methyl acrylate) with benzyl ester of carboxylic acid at the center of the polymer skeletons were synthesized by living radical polymerization for developing a new type of radiation resist with high resistivity to plasma etching and high sensitivity and spatial resolution to ionizing radiations. The initiators were benzyl esters with two functional groups for living radical polymerization on the benzyl and the carboxylic sides. Introduction of benzyl ester to the polymer skeletons changed the polymers from cross-link type to scission type upon γ-irradiation. Irradiation of the polymers resulted in the binary change of the molecular weight, due to dissociative capture of secondary electrons by the benzyl ester, as MnR1 COOCH (C6H5)R2Mn +e- →MnR1COO- + rad CH (C6H5)R2Mn . The generated polymer fragments were not decomposed by further irradiation, which suggests that the synthesized polymers have high resistivity to plasma etching.

  11. Radiation-cured polymeric nanocomposites of enhanced surface-mechanical properties

    NASA Astrophysics Data System (ADS)

    Gläsel, H.-J.; Bauer, F.; Hartmann, E.; Mehnert, R.; Möbus, H.; Ptatschek, V.

    2003-08-01

    Though polymerisation-active metallo-organic nanoparticles have proven exceedingly efficient in modifying the viscoelastic properties of UV and EB crosslinked polymeric nanocomposites, they are obviously unsuitable for practical applications. Rather, adequate polymerisation-activity was imparted on inorganic nanoparticles, e.g. silica and alumina, by grafting onto them functionalised trialkoxysilanes, yielding covalent-bonded, hydrolysis-stable surface compounds. Extensive spectroscopic studies of their siloxane structure led to the idea of a core-shell nanocapsule. The polysiloxane shell formed around the inorganic nanoparticle is not only of major importance to the rheological behaviour of the nanodispersion but, moreover, also admits a sufficiently high nanofiller content for a pronounced reinforcement of the nanocomposite coating. In recent work, organophilation of the inorganic nanoparticles could be accomplished by just applying adsorptive means, thus evading the formation of the precarious alcohols and alkyl acrylates. In the event, round milled corundum micro-particles turned out to be efficient synergists in further improving the respective coatings.

  12. Gold-loaded polymeric micelles for computed tomography-guided radiation therapy treatment and radiosensitization.

    PubMed

    Al Zaki, Ajlan; Joh, Daniel; Cheng, Zhiliang; De Barros, André Luís Branco; Kao, Gary; Dorsey, Jay; Tsourkas, Andrew

    2014-01-28

    Gold nanoparticles (AuNPs) have generated interest as both imaging and therapeutic agents. AuNPs are attractive for imaging applications since they are nontoxic and provide nearly three times greater X-ray attenuation per unit weight than iodine. As therapeutic agents, AuNPs can sensitize tumor cells to ionizing radiation. To create a nanoplatform that could simultaneously exhibit long circulation times, achieve appreciable tumor accumulation, generate computed tomography (CT) image contrast, and serve as a radiosensitizer, gold-loaded polymeric micelles (GPMs) were prepared. Specifically, 1.9 nm AuNPs were encapsulated within the hydrophobic core of micelles formed with the amphiphilic diblock copolymer poly(ethylene glycol)-b-poly(ε-capralactone). GPMs were produced with low polydispersity and mean hydrodynamic diameters ranging from 25 to 150 nm. Following intravenous injection, GPMs provided blood pool contrast for up to 24 h and improved the delineation of tumor margins via CT. Thus, GPM-enhanced CT imaging was used to guide radiation therapy delivered via a small animal radiation research platform. In combination with the radiosensitizing capabilities of gold, tumor-bearing mice exhibited a 1.7-fold improvement in the median survival time, compared with mice receiving radiation alone. It is envisioned that translation of these capabilities to human cancer patients could guide and enhance the efficacy of radiation therapy. PMID:24377302

  13. Preparation of thermosensitive membranes by radiation grafting of acrylic acid/ N-isopropyl acrylamide binary mixture on PET fabric

    NASA Astrophysics Data System (ADS)

    Gupta, Bhuvanesh; Mishra, Swaiti; Saxena, Shalini

    2008-05-01

    Thermosensitive membranes were prepared by radiation-induced graft copolymerization of monomers on PET fabrics. A binary mixture of N-isopropyl acrylamide (NIPAAm) and acrylic acid (AA) was grafted on polyester fabric as a base material to introduce thermosensitive poly( N-isopropyl acrylamide) pendant chains having LCST slightly higher than 37 °C in the membrane. The influence of ferrous sulfate, radiation dose and monomer composition on the degree of grafting was studied. The structure of the grafted fabric was characterized by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The thermosensitive nature of the fabric was monitored by swelling at different temperatures. The graft copolymerization of AA with NIPAAm enhanced the LCST of the resultant membrane to ˜37 °C. The moisture vapor transmission rate (MVTR) and air permeability of the fabric decreased slightly, may be due to the slight blocking of the fabric pores. The immobilization of tetracycline hydrochloride as the model drug and its release characteristics at different temperatures were monitored.

  14. Radiation-induced graft copolymerization of poly(ethylene glycol) monomethacrylate onto deoxycholate-chitosan nanoparticles as a drug carrier

    NASA Astrophysics Data System (ADS)

    Pasanphan, Wanvimol; Rattanawongwiboon, Thitirat; Rimdusit, Pakjira; Piroonpan, Thananchai

    2014-01-01

    Poly(ethylene glycol) monomethacrylate-grafted-deoxycholate chitosan nanoparticles (PEGMA-g-DCCSNPs) were successfully prepared by radiation-induced graft copolymerization. The hydrophilic poly(ethylene glycol) monomethacrylate was grafted onto deoxycholate-chitosan in an aqueous system. The radiation-absorbed dose is an important parameter on degree of grafting, shell thickness and particle size of PEGMA-g-DCCSNPs. Owing to their amphiphilic architecture, PEGMA-g-DCCSNPs self-assembled into spherical core-shell nanoparticles in aqueous media. The particle size of PEGMA-g-DCCSNPs measured by TEM varied in the range of 70-130 nm depending on the degree of grafting as well as the irradiation dose. Berberine (BBR) as a model drug was encapsulated into the PEGMA-g-DCCSNPs. Drug release study revealed that the BBR drug was slowly released from PEGMA-g-DCCSNPs at a mostly constant rate of 10-20% in PBS buffer (pH 7.4) at 37 °C over a period of 23 days.

  15. Hemocompatibility improvement of poly(ethylene terephthalate) via self-polymerization of dopamine and covalent graft of zwitterions.

    PubMed

    Cai, Xianmei; Yuan, Jiang; Chen, Shuangchun; Li, Pengfei; Li, Li; Shen, Jian

    2014-03-01

    Poly (ethylene terephthalate) (PET) has been widely adopted as a scaffold biomaterial, but further hemocompatibility improvement is still needed for wide biomedical applications. Inspired by the composition of adhesive proteins in mussels, we propose to use self-polymerized dopamine to form a surface-adherent polydopamine layer onto PET sheet, followed by Michael addition with N,N-dimethylethylenediamine (DMDA) to build tertiary amine, and final zwitterions(sulfobetaine and carboxybetaine) construction through ring-opening reaction. Physicochemical properties of substrates were demonstrated by water contact angle measurement, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The hemocompatibility was evaluated by platelet adhesion, hemolytic, and protein adsorption. The results showed that the zwitterions immobilized PET endowed with improved resistance to nonspecific protein adsorption and platelet adhesion as well as nonhemolytic. The zwitterions with desirable hemocompatibility can be readily tailored to catheter for various biomedical applications. PMID:24433885

  16. Nylon 6 water-permeable membranes prepared by electron beam radiation-induced graft copolymerization

    SciTech Connect

    Harugy, Y.; Rajbenbach, A.L.

    1981-09-01

    Nylon 6 films, 25 ..mu..m thick, were grafted with polar monomers in aqueous solution following preirradiation with a 550-kV electron beam accelerator. The graft yield rose linearly with grafting period up to 100% graft and leveled off at a graft yield above 150%. At 100 to 200% graft of several acrylic acid derivatives onto the nylon 6 films, water permeation rates comparable to those of PVA and cellophane films were observed. These high water permeation rates of the grafted nylon films were considered as an indication that some of the acrylate copolymers penetrated throughout the matrix of the host polymer. The highest rates of water permeability were observed in nylon acrylamide grafts.

  17. Graft polymerization of wood sawdust and peat with ethylene carbonate. A novel method for the preparation of supports with enhanced mechanical properties to be used in biofiltration of organic vapors.

    PubMed

    Hernández-Meléndez, O; Peydecastaing, J; Bárzana, E; Vaca-Garcia, C; Hernández-Luna, M; Borredon, M E

    2009-01-01

    The graft polymerization reaction between ethylene carbonate (EC) and scots pine sawdust (SPS) or peat moss (PM) offers a solvent-free approach to the simple and inexpensive aliphatic derivatization of these lignocellulosic fibers. This reaction was studied with liquid or vapor EC phases in three different reactor configurations: batch stirred (BSR), semi-continuous stirred (SSR) and continuous tubular in the gas phase (CVTR). The use of a vapor phase allowed a satisfactory grafting yield and minimal production of non-grafted polyol by-products. The crosslinking agent 4,4'-methylenebis(phenylisocyanate) (MDI) achieved superior characteristics to form shaped tablets resistant to water disaggregation, a high water retention capacity and high compression strength, characteristics that conventional organic supports like PM or PM-polyurethane foam mixtures used in biofiltration of waste gases do not completely possess. PMID:18757197

  18. Preparation of surface-imprinted polymer grafted with water-compatible external layer via RAFT precipitation polymerization for highly selective and sensitive electrochemical determination of brucine.

    PubMed

    Zhao, Lijuan; Zhao, Faqiong; Zeng, Baizhao

    2014-10-15

    A novel brucine imprinted polymer was prepared on multi-walled carbon nanotubes by reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization. The polymer was further grafted with hydrophilic poly(glycerol monomethacrylate) brushes to improve its water-compatibility. The obtained molecularly imprinted material showed enhanced accessibility to brucine and improved selective recognition property in water medium. When the material was supported on an ionic liquid functionalized graphene coated glassy carbon electrode for the electrochemical determination of brucine, the resulting electrochemical sensor presented good analytical performance. Under the optimized conditions, the peak current was linear to brucine concentration in the ranges of 0.006-0.6 μM and 0.6-5.0 μM with sensitivities of 15.3 μA/μMmm(2) and 5.4 μA/μM mm(2), respectively; the detection limit was 2 nM (S/N=3). The sensor was successfully applied to the determination of brucine in practical samples and the recovery for the standards added was 94-104%. PMID:24769450

  19. Radiation-induced cationic polymerization of limonene oxide,. cap alpha. -pinene oxide, and. beta. -pinene oxide

    SciTech Connect

    Aikins, J.A.; Williams, F.

    1985-01-01

    After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weights. A high frequency of chain (proton) transfer to monomer is indicated by the fact that the kinetic chain lengths are estimated to be several hundred times larger than the range of DP/sub n/ values (12-4). Structural characterization of the limonene oxide polymer by /sup 1/H and /sup 13/C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the ..cap alpha..-pinene and ..beta..-pinene oxides show that the opening of the epoxide ring for these monomers is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-di-methyl group in the main chain.

  20. Robust Thick Polymer Brushes Grafted from Gold Surfaces Using Bidentate Thiol-Based Atom-Transfer Radical Polymerization Initiators.

    PubMed

    Park, Chul Soon; Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

    2016-03-01

    A new bromoisobutyrate-terminated alkanethiol, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methylpropanoate (BMTBM), was designed as a bidentate adsorbate to form thermally stable bromoisobutyrate-terminated self-assembled monolayers (SAMs) on flat gold surfaces to conduct atom-transfer radical polymerizations (ATRPs). The monolayers derived from BMTBM were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to the monolayers formed from 16-mercaptohexadecyl 2-bromo-2-methylpropanoate (MBM), 16-(3-(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methyl-propanoate (MTBM), and octadecanethiol (C18SH). In this study, although the monolayer derived from BMTBM was less densely packed than those derived from MBM and MTBM, the bidentate adsorbates demonstrated much higher thermal stability in solution-phase thermal desorption tests, owing to the "chelate effect". The enhanced stability of the BMTBM SAMs ensured the development of thick brushes of poly(methyl methacrylate) and polystyrene at elevated temperatures (60, 90, 105, and 120 °C). In contrast, SAMs derived from MBM and MTBM failed to grow polymer brushes at temperatures above 100 °C. PMID:26841087

  1. Radiolytic method of preparation of semiconductor assemblies supported on polymeric membranes

    NASA Astrophysics Data System (ADS)

    Haruvy, Y.; Gratzel, M.; Rajbenbach, L. A.

    Radiation induced grafting of hydrophilic acrylic monomers onto polymeric films and fabric has been employed to prepare supports for catalytic assemblies, which are highly permeable to water and low molecular weight solutes. Transition-metal-oxide semiconductor clusters embedded within the grafted membranes were formed by swelling the membranes with a solution of metal alkoxides followed by gradual hydrolysis. Photolytic methods have been employed to form Pt° clusters onto the semiconductor agregates. Kinetic aspects of the radiation induced grafting of the polymeric supports and the mechanistic features of the preparation of polymer-anchored TiO 2 clusters loaded with Pt° are described. The photocatalytic effectiveness of the TiO 2-Pt assemblies embedded in recoverable polymeric grids was demonstrated in hydrogen generation from aqueous solution and in the degradation of environmental pollutants.

  2. Radiation graft copolymerization of butyl methacrylate and acrylamide onto low density polyethylene and polypropylene films, and its application in wastewater treatment

    NASA Astrophysics Data System (ADS)

    Abdel Ghaffar, A. M.; El-Arnaouty, M. B.; Aboulfotouh, Maysara E.; Taher, N. H.; Taha, Ahmed A.

    2014-09-01

    Butyl methacrylate and acrylamide (BMA/AAm) comonomers were grafted onto low-density polyethylene (LDPE) and polypropylene (PP) films using the mutual gamma radiation grafting technique. The influences of grafting conditions such as solvent, monomer concentration, monomer composition, and irradiation dose on the grafting yield were determined. It was found that using dimethyl formamide as a solvent enhanced the copolymerization process. The grafting yield increases as the comonomer concentration increases up to 60%. Also it was found that the degree of grafting of BMA/AAm onto both LDPE and PP films increases as the AAm content increases till an optimum value at 50:50 wt%. The grafting yield of the comonomers was found to increase with increase in the radiation dose. It was observed that the degree of grafting of polyethylene films is higher than that of polypropylene (PP) films at the same conditions. Some selected properties of the graft copolymers, such as water uptake and thermal properties, were determined using thermogravimetric analysis. The morphology and structure of the grafted films were investigated using scanning electron microscopy, infra-red, and X-ray diffraction. Improvement in such properties of the prepared copolymers was observed which offers possible uses in some practical applications such as the removal of some heavy metals from wastewater. It was found that the maximum metal uptake by the copolymer followed the order Cu2+>Co2+>Ni2+ ions.

  3. Effects of solvents on the radiation grafting reaction of vinyl compounds on poly (3-hydroxybutyrate)

    NASA Astrophysics Data System (ADS)

    Torres, Maykel González; Talavera, José Rogelio Rodríguez; Muñoz, Susana Vargas; Pérez, Manuel González; Castro, Ma. Pilar. Carreón.; Cortes, Jorge Cerna; Muñoz, Rodrigo Alonso Esparza

    2015-03-01

    Vinyl Acetate was grafted onto poly (3-hydroxybutyrate) by the simultaneous gamma irradiation method using different types of solvents and in bulk (solvent free), at 10 kGy and 1.62 kGy/h dose and dose rate respectively. Subsequent complete hydrolysis allowed the conversion of grafted chains from poly (vinyl acetate) to poly (vinyl alcohol). The aim of this study is to determine the effect of solvent through the estimation of the dependence of the degree of grafting with the choice of solvent, the calculation of the degree of crystallinity, and to study the biodegradation of the products. The results showed a greater degree of grafting in bulk, while the more suitable solvent was hexane. Characterization of the grafted copolymer indicated that crystallinity percentage decreased by an increase in grafting, while the biodegradability was promoted by the increment in poly (vinyl alcohol) grafted.

  4. Characterization of Network Structure of Polyacrylamide Based Hydrogels Prepared By Radiation Induced Polymerization

    SciTech Connect

    Mahmudi, Naim; Sen, Murat; Gueven, Olgun; Rendevski, Stojan

    2007-04-23

    In this study network structure of polyacrylamide based hydrogels prepared by radiation induced polymerization has been investigated. Polyacrylamide based hydrogels in the rod form were prepared by copolymerization of acrylamide(AAm) with hydroxyl ethyl methacrylate(HEMA) and methyl acrylamide(MAAm) in the presence of cross-linking agent and water by gamma rays at ambient temperature. Molecular weight between cross-links and effective cross-link density of hydrogels were calculated from swelling as well as shear modulus data obtained from compression tests. The results have shown that simple compression analyses can be used for the determination of effective cross-link density of hydrogels without any need to some polymer-solvent based parameters as in the case of swelling based determinations. Diffusion of water into hydrogels was examined by analyzing water absorption kinetics and the effect of network, structure on the diffusion type and coefficient was discussed.

  5. Semi-interpenetrating polymer networks of poly(3-hydroxybutyrate) prepared by radiation-induced polymerization

    NASA Astrophysics Data System (ADS)

    Martellini, Flavia; Innocentini Mei, Lúcia H.; Lora, Silvano; Carenza, Mario

    2004-09-01

    Semi-interpenetrating polymer networks (IPNs) based on bacterial poly(3-hydroxy butyrate) with a hydrophilic monomer at different compositions were prepared by radiation-induced polymerization using γ-rays from a 60Co source with a total dose of 10-100 kGy. The swelling behaviour was determined by water content at equilibrium, while thermal properties and crystallinity were studied by differential scanning calorimetry. Extraction of the soluble part of PHB from the films at low and high temperature with water or chloroform as well as FTIR data indicate the occurrence of the crosslinking reaction in the hydrogels. The results show a water uptake increasing with the hydrophilic component until 25%.

  6. Physico-chemical aspects of the drugs radiation sterilization in commercial packing (applied scientific problems of radiation pharmaceutical chemistry)

    SciTech Connect

    Safarov, S.A.

    1993-12-31

    The results of studies on the simultaneous radiosterilization of direct and bifurcational trachea prostheses made of silicon-organic rubber of soft elastic consistency, with polyethylenterephthalate and polyamid cuffs, and radiation chemical grafting of polymeric layer and linking with functional groups of the graft sulfanilamide and antibiotics layer are discussed. Radiopharmaceuticals are also described.

  7. Effects of γ-ray radiation grafting on aramid fibers and its composites

    NASA Astrophysics Data System (ADS)

    Zhang, Y. H.; Huang, Y. D.; Liu, L.; Cai, K. L.

    2008-03-01

    Armos fiber was modified by Co 60 γ-ray radiation in the different concentrations' mixtures of phenol-formaldehyde and ethanol. Interlaminar shear strength (ILSS) was examined to characterize the effects of the treatment upon the interfacial bonding properties of Armos fibers/epoxy resin composites. The results showed that the ILSS of the composite, whose fibers were treated by 500 kGy radiation in 1.5 wt% PF, was improved by 25.4%. Nanoindentation technique analysis showed that the nanohardnesses of the various phases (the fiber, the interface and the matrix) in the composite, whose fibers were treated, were correspondingly higher than those in the composite, whose fibers were untreated. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectrum confirmed the increase in the polar groups at the fibers' surface. Atomic force microscopy (AFM) results revealed that the surface of the fibers treated was rougher than that of the fibers untreated. The wettability of the fibers' surface was also enhanced by the treatment. The conclusion that γ-ray irradiation grafting significantly improved the surface properties of Armos fibers could be drawn.

  8. Application of radiation grafted media for lectin affinity separation and urease immobilization: A novel approach to tumor therapy and renal disease diagnosis

    NASA Astrophysics Data System (ADS)

    Müller-Schulte, D.; Daschek, W.

    1995-09-01

    Carriers modified by synergistic radiation grafting are used as affinity media for the separation of a lectin from a mistletoe extract. The grafted supports show distinctly superior properties when compared to conventional affinity media. The application of these carriers as urease immobilization support incorporated in a conductimetric bioreactor for urea analysis as potential diagnostic device in renal diseases is also described.

  9. Electrospun regenerated cellulose nanofibrous membranes surface-grafted with polymer chains/brushes via the atom transfer radical polymerization method for catalase immobilization.

    PubMed

    Feng, Quan; Hou, Dayin; Zhao, Yong; Xu, Tao; Menkhaus, Todd J; Fong, Hao

    2014-12-10

    In this study, an electrospun regenerated cellulose (RC) nanofibrous membrane with fiber diameters of ∼200-400 nm was prepared first; subsequently, 2-hydroxyethyl methacrylate (HEMA), 2-dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA) were selected as the monomers for surface grafting of polymer chains/brushes via the atom transfer radical polymerization (ATRP) method. Thereafter, four nanofibrous membranes (i.e., RC, RC-poly(HEMA), RC-poly(DMAEMA), and RC-poly(AA)) were explored as innovative supports for immobilization of an enzyme of bovine liver catalase (CAT). The amount/capacity, activity, stability, and reusability of immobilized catalase were evaluated, and the kinetic parameters (Vmax and Km) for immobilized and free catalase were determined. The results indicated that the respective amounts/capacities of immobilized catalase on RC-poly(HEMA) and RC-poly(DMAEMA) nanofibrous membranes reached 78 ± 3.5 and 67 ± 2.7 mg g(-1), which were considerably higher than the previously reported values. Meanwhile, compared to that of free CAT (i.e., 18 days), the half-life periods of RC-CAT, RC-poly(HEMA)-CAT, RC-poly(DMAEMA)-CAT, and RC-poly(AA)-CAT were 49, 58, 56, and 60 days, respectively, indicating that the storage stability of immobilized catalase was also significantly improved. Furthermore, the immobilized catalase exhibited substantially higher resistance to temperature variation (tested from 5 to 70 °C) and lower degree of sensitivity to pH value (tested from 4.0 and 10.0) than the free catalase. In particular, according to the kinetic parameters of Vmax and Km, the nanofibrous membranes of RC-poly(HEMA) (i.e., 5102 μmol mg(-1) min(-1) and 44.89 mM) and RC-poly(DMAEMA) (i.e., 4651 μmol mg(-1) min(-1) and 46.98 mM) had the most satisfactory biocompatibility with immobilized catalase. It was therefore concluded that the electrospun RC nanofibrous membranes surface-grafted with 3-dimensional nanolayers of polymer chains/brushes would be

  10. Enhanced separation performance of PVDF/PVP-g-MMT nanocomposite ultrafiltration membrane based on the NVP-grafted polymerization modification of montmorillonite (MMT).

    PubMed

    Wang, Panpan; Ma, Jun; Wang, Zhenghui; Shi, Fengmei; Liu, Qianliang

    2012-03-13

    A novel hydrophilic nanocomposite additive (PVP-g-MMT), coupling of hydrophilic modifier, self-dispersant, and pore-forming agent (porogen), was synthesized by the surface modification of montmorillonite (MMT) with N-vinylpyrrolidone (NVP) via "grafting from" polymerization in the presence of H(2)O(2)-NH(3)·H(2)O as the initiator, and then the nanocomposite membrane of poly(vinylidene fluoride) (PVDF) and PVP-g-MMT was fabricated by wet phase inversion onto clean glass plates. The existence and dispersion of PVP-g-MMT had a great role on structures, morphologies, surface composition, and chemistry of the as-prepared nanocomposite membranes confirmed by varieties of spectroscopic and microscopic characterization techniques, all of which were the correlated functions of PVP-g-MMT content in casting solution. By using the dead-end filtration of protein aqueous solution, the performance of the membrane was evaluated. It was seen that all of the nanocomposite membranes showed obvious improvement of water flux and proper BSA rejection ratio, compared to the control PVDF membrane. Meanwhile, dynamic BSA fouling resistance and flux recovery properties were also greatly enhanced due to the changes of surface hydrophilicity and morphologies. All the experimental results indicated that the as-prepared PVDF nanocomposite membranes showed better separation performances than the control PVDF membrane. Hopefully, the demonstrated method of hydrophilic nanocomposite additive synthesis would be applied for commonly hydroxyl group-containing inorganic nanoparticles, which was favorable to fabricate hydrophilic nanoparticle-enhanced polymer membranes for water treatment. PMID:22376185

  11. Swelling, ion uptake and biodegradation studies of PE film modified through radiation induced graft copolymerization

    NASA Astrophysics Data System (ADS)

    Kaur, Inderjeet; Gupta, Nitika; Kumari, Vandna

    2011-09-01

    An attempt to develop biodegradable polyethylene film grafting of mixture of hydrophilic monomers methacrylic acid (MAAc) and acrylamide (AAm) onto PE film has been carried out by preirradiation method using benzoyl peroxide as the radical initiator. Since ether linkages are susceptible to easy cleavage during degradation process, PE film was irradiated before the grafting reactions by γ-rays to introduce peroxidic linkages (PE-OO-PE) that offer sites for grafting. The effect of irradiation dose, monomer concentration, initiator concentration, temperature, time and amount of water on the grafting percent was determined. Maximum percentage of grafting of binary mixture (MAAc+AAm), (1792%) was obtained at a total concentration of binary monomer mixture=204.6×10 -2 mol/L ([MAAc]=176.5×10 -2 mol/L, [AAm]=28.1×10 -2 mol/L), [BPO]=8.3×10 -2 mol/L at 100 °C in 70 min. The grafted PE film was characterized by the Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopic (SEM) methods. Some selective properties of grafted films such as swelling studies, ion uptake and biodegradation studies have been investigated. The grafted films show good swelling in water, ion uptake studies shows promising results for desalination of brackish water and the soil burial test shows that PE film grafted with binary monomer mixture degrades up to 47% within 50 days.

  12. Radiation grafting of acrylic and methacrylic acid to cellulose fibers to impart high water sorbency

    SciTech Connect

    Zahran, A.H.; Williams, J.L.; Stannett, V.T.

    1980-04-01

    Acrylic and methacrylic acids have been directly grafted to rayon and cotton using the preirradiation technique with /sup 60/ Co gamma rays. The rate of grafting increased with increasing temperature and monomer concentration, as did the final degree of grafting. The amount and rate of grafting also increased with the total irradiation dose but tended to level off at higher doses, in agreement with the leveling off of the radical content reported previously. Methacrylic acid grafted more and faster than acrylic acid to both rayon and cotton. Methacrylic acid grafted more with rayon than cotton, but acrylic acid gave somewhat similar yields with both fibers. The water abosrbency of the grafted fibers depended strongly on their posttreatment. Decrystallizing with 70% zinc chloride or with hot sodium hydroxidy developed supersorbency. The two treatments in succession, respectively, gave the highest values. Metacrylic acid brought about less sorbency than the corrsponding acrylic acid grafts. Useful levels of grafting and supersorbency could be readily and practically achieved by the methods described.

  13. Effect of solvents on the radiation-induced polymerization of ethyl and isopropyl vinyl ethers. [gamma rays

    SciTech Connect

    Hsieh, W.C.; Kubota, H.; Squire, D.R.; Stannett, V.

    1980-09-01

    The radiation-induced cationic polymerization of ethyl and isopropyl vinyl ethers was studied in a variety of solvents. The propagation rate constants were estimated and found to vary widely with the nature of the solvent. In particular, a good linear relationship existed between the logarithms of the rate constants and the reciprocal of the dielectric constants. The lowest rates were those of the highest dielectric constant solvents. These results have been interpreted in terms of the Laidler and Eyring theory of ion-molecule reactions. Isopropyl vinyl ether polymerizes much faster than ethyl vinyl ether, although the rates approach the same value at infinite dielectric constant. In contrast, free carbenium ion polymerizations initiated by stable carbenium ion salts in methylene chloride solution had similar values for both monomers. A comparison is made between the rate constants obtained with both methods of initiation.

  14. Comparative studies on PADC polymeric detector treated by gamma radiation and Ar ion beam

    NASA Astrophysics Data System (ADS)

    El-Saftawy, A. A.; Abdel Reheem, A. M.; Kandil, S. A.; Abd El Aal, S. A.; Salama, S.

    2016-05-01

    In the present study, a comparative analysis and evaluation of the induced defects in polyallyl diglycol carbonate (PADC) polymeric detector exposed to Ar+ and gamma radiation were made. To get insight into the structure defects due to irradiation, X-ray diffraction (XRD) technique was employed. The PADC surface structure changed after irradiation due to the reduction in the surface crystalline structure and the formation of disordered systems. Also, surface morphology changes were traced using scanning electron microscopy (SEM) and showed minor surface irregularities after gamma irradiation and large changes upon Ar+ irradiation. Additionally, micro-hardness and friction coefficient of the irradiated samples were investigated and found to increase after irradiation. UV-vis spectroscopy was used to estimate the optical band gap energy which considered as the basis for calculating the number of conjugated carbon atoms responsible for the blackening effect and color changes took place over the PADC surface. It was found that as the applied dose increased, the band gap decreased and the number of carbon clusters get larger. The refractive index and the dispersion parameters for the studied polymer were calculated and discussed. Also, the induced defects on the polymer surface which serve as a non-radiative centers resulting in reduced photoluminescence (PL) intensity. For nearly all the measured parameters, gamma irradiated samples showed a significant changes compared to that induced by ions. But, low energy Ar+ prove efficiency in controlling surface properties of PADC polymer without affecting its sensitive bulk properties, besides that the obtained results are reasonable and comparable to that induced by gamma radiation.

  15. Pre-irradiation-induced graft reaction of maleic anhydride onto polypropylene

    NASA Astrophysics Data System (ADS)

    Tan, X. M.; Xu, Y. S.; Wang, C. L.

    2006-09-01

    The radiation induced graft polymerization is a well-known method to obtain new materials. Until recently, only conventional radiation sources, such as Co-60 and electron beams, were used. Moreover, part of the damage induced in polymers by heavy ions can produce active sites (peroxides and hydroperoxides) that are useful to initiate grafting reactions. Maleic anhydride (MAH) was grafted onto polypropylene (PP) wax with a number-average molecular weight (Mn) of 8000 by gamma pre-irradiation technique. Effects of total dose, monomer concentration, reaction time, and temperature on percentage of grafting are studied in detail. It is shown that the optimum conditions for grafting are temperature of 70 degrees C and total dose of 14.4 kGy. PP-g-MAH is characterized by infrared spectrum. Differential scanning calorimetry shows that the compatibility of PP-g-MAH is better than that of PP.

  16. Radiation grafting of acrylamide onto starch-filled low density polyethylene

    NASA Astrophysics Data System (ADS)

    Bagheri, Rouhallah; Naimian, Franak; Sheikh, Nassrin

    1997-04-01

    Acrylamide (AAm) was grafted on the surface of starch-filled low density polyethylene (SLDPE) and low density polyethylene (LDPE) films by the mutual irradiation technique at doses from 0.75 to 5 kGy. The effect of dose, solvents and dihydroxybenzoquinone on the degree of grafting was studied by Fourier transform infrared spectroscopy and the weight measurement method of extracted films at a constant monomer concentration (10% w/w). An ultraviolet spectrophotometer was also used to elucidate the results of the above methods. Grafting on SLDPE and LDPE samples reaches a maximum followed by a slight decrease with increasing dose. A higher degree of grafting was obtained on SLDPE samples compared with that on LDPE. An induction period was observed in the case of the samples prepared in tetrahdyrfuran (THF) as the solvent compared with those in chloroform. Addition of benzene to chloroform and THF (50% v/v) accelerates the rate of AAm grafting on the samples. Dihydroxybenzoquinone inhibits the grafting reactions of the samples especially in the THF solutions. The water uptake measurement of the samples correlates with the degree of grafting.

  17. Radiation-grafting of N-vinylimidazole onto silicone rubber for antimicrobial properties

    NASA Astrophysics Data System (ADS)

    Meléndez-Ortiz, H. Iván; Alvarez-Lorenzo, Carmen; Burillo, Guillermina; Magariños, Beatriz; Concheiro, Angel; Bucio, Emilio

    2015-05-01

    Poly(N-vinylimidazole) (PVIm) was grafted numbers onto silicone rubber (SR) with the aim of providing antimicrobial properties. The grafting was carried out by means of gamma rays using the direct method. The influence on the grafting yield of absorbed dose, monomer concentration, addition of FeSO4 salt, composition and type of solvent (H2O, MeOH, THF, and acetone) was investigated. Grafts onto SR between 10% and 90% were obtained at doses from 20 to 100 kGy and a dose rate 10.9 kGy h-1; grafting yield increased with monomer concentration and dose. The new graft copolymers were confirmed by Fourier transform infrared spectroscopy (FT-IR). Differential scanning calorimeter (DSC) showed glass transition at 149 and 159 °C for 38% and 88% grafting respectively. Thermogravimetry analysis (TGA) presented two decomposition temperatures for SR-g-VIm at 380 (PVIm) and 440 °C (SR). SR-g-VIm showed antibacterial activity against Pseudomonas aeruginosa.

  18. Thermoresponsive poly[tri(ethylene glycol) monoethyl ether methacrylate]-peptide surfaces obtained by radiation grafting-synthesis and characterisation.

    PubMed

    Adamus, A; Komasa, J; Kadłubowski, S; Ulański, P; Rosiak, J M; Kawecki, M; Klama-Baryła, A; Dworak, A; Trzebicka, B; Szweda, R

    2016-09-01

    This report demonstrates the feasibility of radiation grafting for the preparation of polymer layers functionalised with short peptide ligands which promote cell adhesion. Thermoresponsive poly [tri(ethylene glycol) monoethyl ether methacrylate] (PTEGMA) layers were synthesised on a polypropylene substrate by post-irradiation grafting. A cell adhesion moiety, the CF-IKVAVK peptide modified with a methacrylamide function and a fluorescent label were introduced to the surface during the polymerisation process. The amount of CF-IKVAVK was easily controlled by changing its concentration in the reaction mixture. The changes in the surface composition, morphology, philicity and thickness at each step of the polypropylene functionalisation confirmed that the surface modification procedures were successful. The increase in environmental temperature above the cloud point temperature of PTEGMA caused a decrease in surface philicity. The obtained PTEGMA and PTEGMA-peptide surfaces above TCP were tested as scaffolds for fibroblast sheet culture and temperature induced detachment. PMID:27182653

  19. Polymeric Materials With Additives for Durability and Radiation Shielding in Space

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard

    2011-01-01

    Polymeric materials are attractive for use in space structures because of their light weight and high strength In addition, polymers are made of elements with low atomic numbers (Z), primarily carbon (C), hydrogen (H), oxygen (0), and nitrogen (N) which provide the best shielding from galactic cosmic rays (GCR) (ref. 1). Galactic cosmic rays are composed primarily of nuclei (i.e., fully ionized atoms) plus a contribution of about 2% from electrons and positrons. There is a small but significant component of GCR particles with high charge (Z > 10) and high energy (E >100 GeV) (ref. 2). These so-called HZE particles comprise only 1 to 2% of the cosmic ray fluence but they interact with very high specific ionization and contribute 50% of the long- term dose to humans. The best shield for this radiation would be liquid hydrogen, which is not feasible. For this reason, hydrogen-containing polymers make the most effective practical shields. Moreover, neutrons are formed in the interactions of GCR particles with materials. Neutrons can only lose energy by collisions or reactions with a nucleus since they are uncharged. This is a process that is much less probable than the Coulombic interactions of charged particles. Thus, neutrons migrate far from the site of the reaction in which they were formed. This increases the probability of neutrons reaching humans or electronic equipment. Fast neutrons (> 1 MeV) can interact with silicon chips in electronic equipment resulting in the production of recoil ions which can cause single event upsets (SEU) in sensitive components (ref. 3). Neutrons lose energy most effectively by elastic collisions with light atoms, particularly hydrogen atoms. Therefore, hydrogen-containing polymers are not only effective in interacting with GCR particles; they are also effective in reducing the energy of the neutrons formed in the interactions.

  20. Studies of composite ion exchange membranes formed from gamma radiation initiated formed from gamma radiation initiated grafting of polymers to modified expanded teflon membranes

    SciTech Connect

    Blubaugh, E.A.; Ramos, B.L.; Heineman, W.R.

    1995-12-31

    This report will present our results for evaluating expanded Teflon as a matrix for polymer grafting. The porosity of the ePTFE starting material was kept constant. However, the volume percent of monomer to solvent and the radiation dosage levels were varied. Also, the monomers used were styrene and (2-dimethylaminoethyl methacrylate) and the influence on the microscopic characteristics of the composite polymers was evaluated via gravimetric determinations and Scanning Electron Microscopy (SEM), respectively. The grafted polystyrene or poly-(2-dimethylaminoethyl methacrylate) must be further modified chemically. The polystyrene must be sulfonated and the poly-(2-dimethylaminoethyl methacrylate) must be quatemized via 2-Bromobutane. These chemical modifications convert the polystyrene into polystyrene-sulfonate (a cation exchanger) and the conversion of poly-(2-dimethylaminoethyl methacrylate) to poly-(2-dimethyl-butyl ammonium ethyl methacrylate) bromide (an anion exchange medium). These polymer composites were evaluated as to their ion-exchange ability, via the electrochemical activity displayed through exchanged electroactive ions.

  1. A gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters

    NASA Astrophysics Data System (ADS)

    Babic, S.; Park, Y. S.; Schreiner, L. J.

    2004-01-01

    In this presentation we show results of investigations on gelatin-free dosimeters containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide (named Aqueous Polyacrylamide, APA, dosimeters). The dosimeters were prepared with three different total monomer concentrations (2, 6, and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all three dosimeters, show a continuous degree of polymerization over the range of dose 0.5 - 25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of cross-linked polymer formed at each dose. This model may be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

  2. Synthesis and characterization of β-CD-coated polystyrene microspheres by γ-ray radiation emulsion polymerization.

    PubMed

    Xu, Dezhi; Wang, Mozhen; Ge, Xuewu; Lam, Michael Hon-Wah

    2012-11-23

    Polystyrene (PS) microspheres coated with β-cyclodextrin (β-CD) were fabricated via γ-ray-induced emulsion polymerization in a ternary system of styrene/β-CD/water (St/β-CD/water). The solid inclusion complex of St and β-CD particles formed at the St droplets-water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β-CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β-CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β-CD content even to 36°. Thus, this work provides a new and one-pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization. PMID:22887797

  3. Engineered Water Highways in Fuel Cells: Radiation Grafting of Gas Diffusion Layers.

    PubMed

    Forner-Cuenca, Antoni; Biesdorf, Johannes; Gubler, Lorenz; Kristiansen, Per Magnus; Schmidt, Thomas Justus; Boillat, Pierre

    2015-11-01

    A novel method to produce gas diffusion layers with patterned wettability for fuel cells is presented. The local irradiation and subsequent grafting permits full design flexibility and wettability tuning, while modifying throughout the whole material thickness. These water highways have improved operando performance due to an optimized water management inside the cells. PMID:26395373

  4. Skin graft

    MedlinePlus

    Skin transplant; Skin autografting; FTSG; STSG; Split thickness skin graft; Full thickness skin graft ... site. Most people who are having a skin graft have a split-thickness skin graft. This takes ...

  5. Radiation-induced reduction-polymerization route for the synthesis of PEDOT conducting polymers

    NASA Astrophysics Data System (ADS)

    Cui, Zhenpeng; Coletta, Cecilia; Rebois, Rolando; Baiz, Sarah; Gervais, Matthieu; Goubard, Fabrice; Aubert, Pierre-Henri; Dazzi, Alexandre; Remita, Samy

    2016-02-01

    Synthesis of conducting poly(3,4-ethylenedioxythiophene), PEDOT, is achieved through an original reduction-polymerization route: γ-radiolysis of aqueous solutions containing EDOT monomers under N2 atmosphere. According to UV-vis absorption spectrophotometry and ATR-FTIR spectroscopy, reduction of EDOT is initiated by hydrated electrons produced by water radiolysis and leads to PEDOT polymers through coupling reactions. The morphology of PEDOT is characterized by Cryo- TEM microscopy in aqueous solution and by SEM after deposition. In an original way, high resolution AFM microscopy, coupled with infrared nanospectroscopy, is used to probe the local chemical composition of PEDOT nanostructures. The results demonstrate that spherical self-assembled PEDOT nanostructures are formed. TGA analysis and four point probe measurements demonstrate that thermal stability and electrical conductivity of PEDOT polymers obtained by the present original reduction-polymerization method are close to those of PEDOT we previously prepared by radiolysis according to an oxidation-polymerization route.

  6. Evaluation of Thermal Control Coatings and Polymeric Materials Exposed to Ground Simulated Atomic Oxygen and Vacuum Ultraviolet Radiation

    NASA Technical Reports Server (NTRS)

    Kamenetzky, R. R.; Vaughn, J. A.; Finckenor, M. M.; Linton, R. C.

    1995-01-01

    Numerous thermal control and polymeric samples with potential International Space Station applications were evaluated for atomic oxygen and vacuum ultraviolet radiation effects in the Princeton Plasma Physics Laboratory 5 eV Neutral Atomic Oxygen Facility and in the MSFC Atomic Oxygen Drift Tube System. Included in this study were samples of various anodized aluminum samples, ceramic paints, polymeric materials, and beta cloth, a Teflon-impregnated fiberglass cloth. Aluminum anodizations tested were black duranodic, chromic acid anodize, and sulfuric acid anodize. Paint samples consisted of an inorganic glassy black paint and Z-93 white paint made with the original PS7 binder and the new K2130 binder. Polymeric samples evaluated included bulk Halar, bulk PEEK, and silverized FEP Teflon. Aluminized and nonaluminized Chemfab 250 beta cloth were also exposed. Samples were evaluated for changes in mass, thickness, solar absorptance, and infrared emittance. In addition to material effects, an investigation was made comparing diffuse reflectance/solar absorptance measurements made using a Beckman DK2 spectroreflectometer and like measurements made using an AZ Technology-developed laboratory portable spectroreflectometer.

  7. Synthesis of high-molecular-weight polymer of methyl chloride salt of N,N-dimethylaminoethyl methacrylate by radiation-induced polymerization at high pressure. [Gamma radiation

    SciTech Connect

    Ishigaki, I.; Okada, T.; Sasuga, T.; Takehisa, M.; Machi, S.

    1981-02-01

    Polymer of the methyl chloride salt of N,N-dimethylaminoethyl methacrylate and its copolymer with acrylamide are used as cationic flocculants for the treatment of waste water containing organic suspensions. As reported, radiation-induced polymerization is one of the most convenient methods because of its temperature independence of initiation and extremely large G-value. In general, a flocculant with higher molecular weight has larger flocculation effects. The high-molecular-weight products were prepared in high monomer concentration and a low dose rate. This paper concerns the polymerization and copolymerization of methyl chloride salt of N,N-dimethylaminoethyl methacrylate at high pressure, up to 7000 kg/cm/sup 2/, providing high-molecular-weight cationic flocculants.

  8. In-situ polymerization of vinyl pyrrolidinone on nylon 66 by gamma radiation

    SciTech Connect

    Hsieh, Y.L.; Potter, D.; Ellison, M.S.

    1984-10-01

    The polymerization of vinyl pyrrolidinone on nylon 66, with the assistance of aqueous phenol and formic acid, was investigated by mutual and post irradiation procedures. Both solvents were found to greatly facilitate the polymerization with the post irradiation procedure, whereas neither presented any advantage with the mutual irradiation procedure. Tensile properties of the modified fibers were affected in similar ways by both the irradiation procedures and solvents in that the only notable changes were the somewhat higher extensions at yield and at break. The moisture regain values of the treated yarns and fabrics were increased up to three-fold. Surface morphology of the modified fibers was revealed by SEM.

  9. A mild method of amine-type adsorbents syntheses with emulsion graft polymerization of glycidyl methacrylate on polyethylene non-woven fabric by pre-irradiation

    NASA Astrophysics Data System (ADS)

    Ma, Hongjuan; Yao, Side; Li, Jingye; Cao, Changqing; Wang, Min

    2012-09-01

    A mild pre-irradiation method was used to graft glycidyl methacrylate (GMA) onto polyethylene (PE) non-woven fabric (NF). The polymer was irradiated by electron beam in air atmosphere at room temperature. The degree of grafting (Dg) was determined as a function of reaction time, absorbed dose, monomer concentration and temperature. After 30 kGy irradiation, with 5% GMA, surfactant Tween 20 (Tw-20) of 0.5% at 55 °C for 15 min, the trunk polymer was made grafted with a Dg of 150%. Selected PE-g-PGMA of different Dg was modified with aminated compounds such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). The obtained amine-type adsorbents were prepared to remove copper and uranium ions from solution. It was shown that at least 90% of copper and 60% of uranium with the initial concentration from 3 to 1000 ppb can be removed from water.

  10. Gamma-ray co-irradiation induced graft polymerization of NVP and SSS onto polypropylene non-woven fabric and its blood compatibility

    NASA Astrophysics Data System (ADS)

    Li, Rong; Wang, Hengdong; Wang, Wenfeng; Ye, Yin

    2013-10-01

    Sodium styrenesulfonate was grafted onto PPNWF via γ-ray co-irradiation method with the existence of N-vinyl-2-pyrrolidone. The effect of absorbed dose, dose rate and concentration of binary monomer on the degree of grafting was investigated. The surface chemical change was characterized by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The wettability was characterized through the measurement of adsorption percentage of water and phosphate buffer solution (PBS). The result demonstrated that the grafted poly(NVP-co-SSS) chains can improve the hydrophilicity of PPNWF. Furthermore, the modified PPNWF has good blood compatibility, such as low hemolysis rate, low platelet adhesion and effectively extending the blood coagulation times. Consequently, hydrophilicity and hemocompatibility of PPNWF were greatly enhanced by the immobilization of poly(NVP-co-SSS) chains.

  11. Fire proofing by radiation grafting (application on polyester and polypropylene). Scientific technical report

    SciTech Connect

    Hill, B.J.; Einsele, U.; Di Modica, G.; Wattiez, D.

    1980-01-01

    This report outlines efforts to try out a modern technique, radition grafting, rather than chemical and heat fixation, to make textiles more fire-proof by reducing as much as possible the deterioration in conventional properties, in particular softness and handle, to which the former give rise. The expected consequences are twofold: possession of a general method for fire-proofing textile materials which retain the conventional initial characteristics more fully, and improvement of the durability of the fire-proof properties.

  12. Radiation-induced graft copolymerization of dimethylaminoethyl methacrylate onto graphene oxide for Cr(VI) removal

    NASA Astrophysics Data System (ADS)

    Ma, Hui-Ling; Zhang, Youwei; Zhang, Long; Wang, Liancai; Sun, Chao; Liu, Pinggui; He, Lihua; Zeng, Xinmiao; Zhai, Maolin

    2016-07-01

    Dimethylaminoethyl methacrylate (DMAEMA)-grafted graphene oxide hybrid materials (GO-g-P) were fabricated using γ-ray irradiation at ambient temperature. The morphology and structure of GO-g-P were characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron (XPS), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). It was confirmed that DMAEMA was grafted successfully on the surface of graphene sheet. The grafting yield of GO-g-P increased with monomer concentration (0-2.5 mol L-1) and dose (0-40 kGy). The resulting adsorbent (GO-g-P) with amine groups was highly efficient for removing Cr(VI) from its acidic aqueous solution and could be easily separated by filtration. The optimum pH for Cr(VI) removal was observed at pH 1.1 and the Cr(VI) uptake of GO-g-P at this pH was 82.4 mg g-1.

  13. Mechanical properties of tough hydrogels synthesized with a facile simultaneous radiation polymerization and cross-linking method

    NASA Astrophysics Data System (ADS)

    Jiang, Fangzhi; Wang, Xuezhen; He, Changcheng; Saricilar, Sureyya; Wang, Huiliang

    2015-01-01

    Radiation-induced polymerization and cross-linking method has been applied to hydrogel preparations for decades, but less attention has been paid to the mechanical properties of the hydrogels. In this work, we provide a systematic study on the mechanical properties of hydrogels synthesized with the simultaneous radiation polymerization and cross-linking method. The prepared polyacrylamide (PAAm) had very good mechanical properties, namely high compressive strengths (several to more than 10 MPa), high tensile strengths (up to 260 kPa), high fracture strains (up to 12) and high fracture energies (10-160 J/m2). Absorbed dose and monomer concentration were the two important factors affecting the mechanical properties of the gels. The compressive strength and elastic modulus of the gels increased with increasing absorbed dose and monomer concentration, while the tensile strength, fracture strain and fracture energy of the gels decreased with increasing absorbed dose. The gels also showed excellent elastic recovery property, as indicated by the low stress-strain hysteresis ratios in cyclic tensile tests as well as the small loss factors measured with dynamic mechanical analysis (DMA).

  14. Development of novel hydrogels by modification of sterculia gum through radiation cross-linking polymerization for use in drug delivery

    NASA Astrophysics Data System (ADS)

    Singh, Baljit; Vashishtha, Manu

    2008-05-01

    In order to modify the sterculia gum polysaccharide, to develop the hydrogels meant for the drug delivery, we have prepared sterculia gum, 2-hydroxyethylmethacrylate (HEMA) and acrylic acid (AAc) based hydrogels by radiation-induced crosslinking polymerization. Polymeric networks (hydrogels) thus formed were characterized with SEMs, FTIR,TGA and swelling studies which were carried out as a function monomers concentration, radiation dose, amount of sterculia contents in the polymer matrix and nature of the swelling medium. This paper discusses the swelling kinetics of the hydrogels and release dynamics of anti-diarrhea model drug ornidazole from the hydrogels to evaluation of swelling and drug release mechanism. Diffusion exponent 'n' have 0.73, 0.56 and 0.61 values and gel characteristic constant 'k' have 1.28 × 10-2, 2.95 × 10-2 and 2.14 × 10-2 values in distilled water, pH 2.2 buffer and pH 7.4 buffer. The release of drug from the polymer matrix occurred through non-Fickian diffusion mechanism. The values for the late time diffusion coefficients have been lower than the values of initial and average diffusion coefficients. It reflects that in the initial stages rate of release of drug from polymer matrix was higher as compared to the late stages, it means after certain time the drug release occurred in controlled manner.

  15. Immobilization of glucoamylase on polymer surface by radiation-induced polymerization of glass-forming monomers at low temperatures. [Gamma radiation; 2-hydroxyethyl methacrylate; diethylene glycol dimethacrylate

    SciTech Connect

    Yoshida, M.; Kaetsu, I.

    1981-02-01

    Glucoamylase was immobilized in hydrophilic porous poly(2-hydroxyethyl methacrylate) (PHEMA) and hydrophobic microsphere poly(diethylene glycol dimethyacrylate) (PDGDA) by radiation-induced polymerization at low temperatures, in the presence of acetate buffer solution. The distribution on the matrix of immobilized glucoamylase was investigated using fluorescein isothiocyanate (FITC)-conjugated glucoamylase and the fluorescence microscope. It was found that in the porous PHEMA system, the FITC-conjugated glucoamylase is present mainly on the interface between polymer membrane and pore structure and partly in the polymer, while in the microsphere PDGDA system the immobilized glucoamylase is present merely on the surface of the polymer microsphere.

  16. High-energy radiation processing, a smart approach to obtain PVP-graft-AA nanogels

    NASA Astrophysics Data System (ADS)

    Grimaldi, N.; Sabatino, M. A.; Przybytniak, G.; Kaluska, I.; Bondì, M. L.; Bulone, D.; Alessi, S.; Spadaro, G.; Dispenza, C.

    2014-01-01

    Poly(N-vinylpyrrolidone)-grafted-acrylic acid biocompatible nanogels (NGs) were prepared using an exiting industrial-type electron accelerator and setups, starting from semi-dilute aqueous solutions of a commercial PVP and the acrylic acid monomer. As a result, NGs with tunable size and structure can be obtained quantitatively. Sterility was also imparted at the integrated dose absorbed. The chemical structure of the NGs produced was confirmed through Fourier Transformer Infrared Spectroscopy (FT-IR). The molecular and physico-chemical properties of NGs, such as the hydrodynamic dimensions and surface charge densities, for various polymer and monomer concentrations in the irradiated solutions, are discussed here.

  17. Bone Grafts

    MedlinePlus

    A bone graft transplants bone tissue. Surgeons use bone grafts to repair and rebuild diseased bones in your hips, knees, spine, and sometimes other bones and joints. Grafts can also repair bone loss caused by some ...

  18. New trends of radiation processing applications

    NASA Astrophysics Data System (ADS)

    Machi, Sueo

    1996-03-01

    Major fields of radiation processing applications are: polymeric materials, food processing, sterilization of medical products and environmental conservation. There are about 200 60Co gamma irradiation facilities and 700 electron beam accelerators, mainly for commercial purposes, throughout the world. Radiation cross-linking and grafting techniques of polymeric materials have been providing many unique products including heat materials, heat shrinkable materials, curing of coatings and battery separators. Extensive studies have been devoted to the development of bio-medical materials using radiation processing to prepare bio-compatible materials and controlled release of drugs. New wound dressings have been successfully developed in Poland and Israel for commercial clinical use.

  19. Analysis of low-dose radiation shield effectiveness of multi-gate polymeric sheets

    NASA Astrophysics Data System (ADS)

    Kim, S. C.; Lee, H. K.; Cho, J. H.

    2014-07-01

    Computed tomography (CT) uses a high dose of radiation to create images of the body. As patients are exposed to radiation during a CT scan, the use of shielding materials becomes essential in CT scanning. This study was focused on the radiation shielding materials used for patients during a CT scan. In this study, sheets were manufactured to shield the eyes and the thyroid, the most sensitive parts of the body, against radiation exposure during a CT scan. These sheets are manufactured using silicone polymers, barium sulfate (BaSO4) and tungsten, with the aim of making these sheets equally or more effective in radiation shielding and more cost-effective than lead sheets. The use of barium sulfate drew more attention than tungsten due to its higher cost-effectiveness. The barium sulfate sheets were coated to form a multigate structure by applying the maximum charge rate during the agitator and subsequent mixing processes and creating multilayered structures on the surface. To measure radiation shielding effectiveness, the radiation dose was measured around both eyes and the thyroid gland using sheets in three different thicknesses (1, 2 and 3 mm). Among the 1 and 2 mm sheets, the Pb sheets exhibited greater effectiveness in radiation shielding around both eyes, but the W sheets were more effective in radiation shielding around the thyroid gland. In the 3 mm sheets, the Pb sheet also attenuated a higher amount of radiation around both eyes while the W sheet was more effective around the thyroid gland. In conclusion, the sheets made from barium sulfate and tungsten proved highly effective in shielding against low-dose radiation in CT scans without causing ill-health effects, unlike lead.

  20. Investigation of space radiation effects in polymeric film-forming materials

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.; Jarke, F.

    1975-01-01

    The literature search in the field of ultraviolet radiation effects that was conducted during the previous program, Contract No. NAS1-12549, has been expanded to include the effects of charged particle radiation and high energy electromagnetic radiation. The literature from 1958 to 1969 was searched manually, while the literature from 1969 to present was searched by using a computerized keyword system. The information generated from this search was utilized for the design of an experimental program aimed at the development of materials with improved resistance to the vacuum-radiation environment of space. Preliminary irradiation experiments were performed which indicate that the approaches and criteria employed are very promising and may provide a solution to the challenging problem of polymer stability to combined ultraviolet/high energy radiation.

  1. Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

    PubMed Central

    Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

    2012-01-01

    This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

  2. Polymeric micelles of amphiphilic graft copolymer of α-tocopherol succinate-g-carboxymethyl chitosan for tamoxifen delivery: Synthesis, characterization and in vivo pharmacokinetic study.

    PubMed

    Jena, Sunil K; Sangamwar, Abhay T

    2016-10-20

    Novel amphiphilic graft copolymers were prepared from low molecular weight carboxymethyl chitosan (LMW Cmc) and α-tocopherol succinate (TS) via an amidation reaction and confirmed by (1)H NMR and IR spectroscopy. These graft copolymers are self-assembled to nanosized core-shell-structural micelles in an aqueous milieu. The critical micelle concentration (CMC) decreased with an increasing substitution of TS on LMW Cmc, which ranged from 7.94×10(-8) to 1.58×10(-6)g/mL. Cmc-TS4.5 (Cmc-TS with a charged molar ratio of TS to glucosamine units of Cmc∼4.5) was shown maximum TMX loading up to 8.08±0.98%. Both blank and TMX-loaded PM's of Cmc-TS4.5 exhibit spherical shape with particle size below 200nm. An in vitro release study in simulated gastric and intestinal fluid demonstrated that TMX release from TMX-PM4.5 (TMX-PMs prepared with amphiphilic polymer Cmc-TS4.5, and the weight ratio of Cmc-TS4.5 to TMX was 8:1) was slow and pH dependent. In vivo oral absorption study revealed Cmc-TS4.5 based PM's permeated the epithelial barrier via the paracellular route without causing any intestinal damage. In vivo toxicity study demonstrated the safety of PM's after oral administration. Compared to tamoxifen control, TMX-PM4.5 dosed to fasted female Sprague Dawley rats showed a 1.9 fold increase in AUC0-72h. Thus, the results suggested that Cmc-TS micelles are a promising carrier for TMX delivery. PMID:27474667

  3. Radiation-induced and RAFT-mediated grafting of poly(hydroxyethyl methacrylate) (PHEMA) from cellulose surfaces

    NASA Astrophysics Data System (ADS)

    Kodama, Yasko; Barsbay, Murat; Güven, Olgun

    2014-01-01

    This paper presents the results of RAFT mediated free-radical graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto cellulose fibers in a "grafting-from" approach under γ-irradiation. The effects of absorbed dose and monomer concentration on the graft ratios were investigated at different monomer (HEMA) to RAFT agent (cumyl dithiobenzoate, CDB) ratios. Cellulose-g-PHEMA copolymers with various graft ratios up to 92% (w/w) have been synthesized. The synthesized copolymers were characterized by ATR-FTIR spectroscopy, X-ray photoelectron spectroscopy, elemental analysis and scanning electron microscopy. The results of various techniques confirmed the existence of PHEMA in the copolymer composition.

  4. SYNTHESIS AND IN VITRO CHARACTERIZATION OF HYDROXYPROPYL METHYLCELLULOSE-GRAFT-POLY (ACRYLIC ACID/2-ACRYLAMIDO-2-METHYL-1-PROPANESULFONIC ACID) POLYMERIC NETWORK FOR CONTROLLED RELEASE OF CAPTOPRIL.

    PubMed

    Furqan Muhammad, Iqbal; Mahmood, Ahmad; Aysha, Rashid

    2016-01-01

    A super-absorbent hydrogel was developed by crosslinking of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and acrylic acid with hydroxypropyl methylcellulose (HPMC) for controlled release drug delivery of captopril, a well known antihypertensive drug. Acrylic acid and AMPS were polymerized and crosslinked with HPMC by free radical polymerization, a widely used chemical crosslinking method. N,N'-methylenebisacrylamide (MBA) and potassium persulfate (KPS) were added as cross-linker and initiator, respectively. The hydrogel formulation was loaded with captopril (as model drug). The concentration of captopril was monitored at 205 nm using UV spectrophotometer. Equilibrium swelling ratio was determined at pH 2, 4.5 and 7.4 to evaluate the pH responsiveness of the formed hydrogel. The super-absorbent hydrogels were evaluated by FTIR, SEM, XRD, and thermal analysis (DSC and TGA). The formation of new copolymeric network was determined by FTIR, XRD, TGA and DSC analysis. The hydrogel formulations with acrylic acid and AMPS ratio of 4: 1 and lower amounts of crosslinker had shown maximum swelling. Moreover, higher release rate of captopril was observed at pH 7.4 than at pH 2, because of more swelling capacity of copolymer with increasing pH of the aqueous medium. The present research work confirms the development of a stable hydrogel comprising of HPMC with acrylic acid and AMPS. The prepared hydrogels exhibited pH sensitive behav-ior. This superabsorbent composite prepared could be a successful drug carrier for treating hypertension. PMID:27008813

  5. Chronic graft-versus-host disease in the rat radiation chimera. III. Immunology and immunopathology in rapidly induced models

    SciTech Connect

    Beschorner, W.E.; Tutschka, P.J.; Santos, G.W.

    1983-03-01

    Although chronic graft-versus-host disease (GVHD) frequently develops in the long-term rat radiation chimera, we present three additional models in which a histologically similar disease is rapidly induced. These include adoptive transfer of spleen and bone marrow from rats with spontaneous chronic GVHD into lethally irradiated rats of the primary host strain; sublethal irradiation of stable chimeras followed by a booster transplant; and transfer of spleen cells of chimeras recovering from acute GVHD into second-party (primary recipient strain) or third-party hosts. Some immunopathologic and immune abnormalities associated with spontaneous chronic GVHD were not observed in one or more of the induced models. Thus, IgM deposition in the skin, antinuclear antibodies, and vasculitis appear to be paraphenomena. On the other hand, lymphoid hypocellularity of the thymic medulla, immaturity of splenic follicles, and nonspecific suppressor cells were consistently present in the long term chimeras, and in all models. These abnormalities therefore may be pathogenetically important, or closely related to the development of chronic GVHD.

  6. Hydrocarbon compositions containing polyolefin graft polymers

    SciTech Connect

    Kapuscinski, M.M.; Liu, C.S.; Hart, W.P.; Grina, L.D.

    1987-02-03

    A graft polymer is described comprising an oil-soluble, substantially linear, carbon-carbon backbone polymer having graft polymerized thereon units derived from, as a functional monomer, the reaction product of (i) an unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring. The graft polymer is also described wherein the backbone polymer is a copolymer of ethylene-propylene or a terpolymer of ethylene-propylene-diene monomer.

  7. Methods of fiber surface grafting for interphase design and tailored composite response

    NASA Astrophysics Data System (ADS)

    Arnold, Jesse Judson

    1997-11-01

    The objective of this research was to develop methods of fiber surface grafting for interphase formation, and to experimentally evaluate and model these interphases in order to further elucidate their role in fiber-reinforced composites. Surface modification by sp{60}Co gamma irradiation was used initially to graft acrylic polymers on the surface of ultra-high modulus (UHMPE) fibers. This technique utilized low dose rates and low total doses, and achieved grafting with retention of the exceptional UHMPE properties. The surface properties of the fibers were evaluated using fourier transform infra-red spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), and mechanical tests and dynamic mechanical spectrometry (DMS) of discontinuous fiber composites. Depending on the glass transition temperature, Tg, and chemical structure of the graft, the fiber/matrix adhesion and the interfacial failure mechanism was tailored to provide either enhanced reinforcement or toughening. Using a three-phase block model, the DMS characteristics of the composites were modeled and the reinforcement efficiencies extrapolated as a function of surface treatment. The model successfully predicts the tan delta response of the composite and the appearance of additional loss dispersions associated with the interphase. However, the interactions between the high-energy gamma radiation and the fiber and grafts yield interphases that are difficult to characterize and control. The hydroperoxidation grafting method was subsequently developed, which permitted the grafting of tethered, linear chains by a free radical-type polymerization. Poly(styrene-stat-acrylonitrile) was grafted initially, in which the nitrogen in acrylonitrile was used as a marker to verify grafting and to estimate the grafting efficiency by ESCA analysis. Tapping modesp{TM} atomic force microscopy (TMAFM) images of the grafted fibers revealed a nodular surface topography with dimensions that were correlated to the

  8. Thermal analysis evaluation of mechanical properties changes promoted by gamma radiation on surgical polymeric textiles

    NASA Astrophysics Data System (ADS)

    Ferreira, L. M.; Casimiro, M. H.; Oliveira, C.; Cabeço Silva, M. E.; Marques Abreu, M. J.; Coelho, A.

    2002-05-01

    The large number of surgical operations with post-operative infection problems and the appearing of new infectious diseases, contribute to the development of new materials in order to answer the needs of health care services. This development must take into account the modifications promoted by sterilisation methods in materials, namely by gamma radiation. The differential scanning calorimetry (DSC) and thermogravimetry (TGA) techniques show that a nonwoven and a laminate textiles maintain a good molecular cohesion, do not showing high levels of degradation, for gamma radiation dose values lower than 100 kGy in nonwoven and 200 kGy in laminate materials. The tensile strength and the elongation decrease slowly for the nonwoven textile and decrease faster for the laminate textile for 25 and 80 kGy absorbed dose. This paper shows that the DSC and TGA techniques can be helpful for the prevision of mechanical changes occurred in the materials as a consequence of the gamma irradiation.

  9. Rapid, facile microwave-assisted synthesis of xanthan gum grafted polyaniline for chemical sensor.

    PubMed

    Pandey, Sadanand; Ramontja, James

    2016-08-01

    Grafting method, through microwave radiation procedure is extremely productive in terms of time consumption, cost effectiveness and environmental friendliness. In this study, conductive and thermally stable composite (mwXG-g-PANi) was synthesized by grafting of aniline (ANi) on to xanthan gum (XG) using catalytic weight of initiator, ammonium peroxydisulfate in the process of microwave irradiation in an aqueous medium. The synthesis of mwXG-g-PANi were confirm by FTIR, XRD, TGA, and SEM. The influence of altering the microwave power, exposure time of microwave, concentration of monomer and the amount of initiator of graft polymerization were studied over the grafting parameters, for example, grafting percentage (%G) and grafting efficiency (%E). The maximum %G and %E achieved was 172 and 74.13 respectively. The outcome demonstrates that the microwave irradiation strategy can increase the reaction rate by 72 times over the conventional method. Electrical conductivity of XG and mwXG-g-PANi composite film was performed. The fabricated grafted sample film were then examined for the chemical sensor. The mwXG-g-PANi, effectively integrated and handled, are NH3 sensitive and exhibit a rapid sensing in presence of NH3 vapor. Chemiresistive NH3 sensors with superior room temperature sensing performance were produced with sensor response of 905 at 1ppb and 90% recovery within few second. PMID:27118045

  10. Synthesis and characterization of photoluminescent hybrids of poly( ɛ-caprolactone)-grafted-polyhedral oligosilsesquioxane by using a combination of ring-opening polymerization and click chemistry

    NASA Astrophysics Data System (ADS)

    Cao, Xuan Thang; Showkat, Ali Md; Bach, Long Giang; Jeong, Yeon Tae; Kim, Jong Soo; Lim, Kwon Taek; Gal, Yeong-Soon

    2015-01-01

    Photoluminescent hybrids of poly( ɛ-caprolactone) (PCL), polyhedral oligosilsesquioxane (POSS) and terbium ions (Tb3+) were synthesized by using a combination of ring-opening polymerization (ROP), click chemistry and coordination chemistry. Initially, acetylene functionalized PCL (alkyne-PCL-COOH) was prepared by using ROP of ɛ-caprolactone with propargyl alcohol, and azide-substituted POSS (POSS-N3) was prepared by using the reaction of chloropropyl-heptaisobutyl-substituted POSS with NaN3. The click reaction between alkyne-PCL-COOH and POSS-N3 afforded POSS-g-PCL, which was subsequently coordinated with Tb3+ ions in the presence of 1,10-phenanthroline to produce POSS-g-PCL-Tb3+-Phen. The structures and compositions of the hybrids were investigated by using 1H nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscope (FE-SEM), Transmission electron microscopy (TEM), and Thermogravimetric analysis (TGA). The optical properties of POSS-g-PCL-Tb3+-Phen complexes were characterized by using photoluminescence spectroscopy, which showed four high emission bands centered at 489, 545, 584, and 620 nm with excitation at 330 nm. The emission spectra of the europium-ion-coordinated hybrids, POSS-g-PCL-Eu3+-Phen, had four high-intensity peaks, 594, 617, 652 and 686 nm, for an excitation wavelength of 352 nm.

  11. Different Resistance to UV-B Radiation of Extracellular Polymeric Substances of Two Cyanobacteria from Contrasting Habitats

    PubMed Central

    Song, Wenjuan; Zhao, Chenxi; Zhang, Daoyong; Mu, Shuyong; Pan, Xiangliang

    2016-01-01

    The effects of UV-B radiation (UVBR) on photosynthetic activity (Fv/Fm) of aquatic Synechocystis sp. and desert Chroococcus minutus and effects on composition and fluorescence property of extracellular polymeric substances (EPSs) from Synechocystis sp. and C. minutus were comparatively investigated. The desert cyanobacterium species C. minutus showed higher tolerance of PSII activity (Fv/Fm) to UVBR than the aquatic Synechocystis sp., and the inhibited PSII activity of C. minutus could be fully recovered while that of Synechocystis sp. could be partly recovered. UVBR had significant effect on the yield and biochemical composition of EPS of both species. Protein-like and humic acid-like substances were detected in EPS from Synechocystis sp., and protein-like and phenol-like fluorescent compounds were detected in EPS from C. minutus. Proteins in EPS of desert and aquatic species were significantly decomposed under UVBR, and the latter was more easily decomposed. The polysaccharides were much more resistant to UVBR than the proteins for both species. Polysaccharides of Synechocystis sp. was degraded slightly but those of C. minutus was little decomposed. The higher tolerance to UVBR of the desert cyanobacterium can be attributed to the higher resistance of its EPS to photodegradation induced by UVBR in comparison with the aquatic species. PMID:27597841

  12. Different Resistance to UV-B Radiation of Extracellular Polymeric Substances of Two Cyanobacteria from Contrasting Habitats.

    PubMed

    Song, Wenjuan; Zhao, Chenxi; Zhang, Daoyong; Mu, Shuyong; Pan, Xiangliang

    2016-01-01

    The effects of UV-B radiation (UVBR) on photosynthetic activity (Fv/Fm) of aquatic Synechocystis sp. and desert Chroococcus minutus and effects on composition and fluorescence property of extracellular polymeric substances (EPSs) from Synechocystis sp. and C. minutus were comparatively investigated. The desert cyanobacterium species C. minutus showed higher tolerance of PSII activity (Fv/Fm) to UVBR than the aquatic Synechocystis sp., and the inhibited PSII activity of C. minutus could be fully recovered while that of Synechocystis sp. could be partly recovered. UVBR had significant effect on the yield and biochemical composition of EPS of both species. Protein-like and humic acid-like substances were detected in EPS from Synechocystis sp., and protein-like and phenol-like fluorescent compounds were detected in EPS from C. minutus. Proteins in EPS of desert and aquatic species were significantly decomposed under UVBR, and the latter was more easily decomposed. The polysaccharides were much more resistant to UVBR than the proteins for both species. Polysaccharides of Synechocystis sp. was degraded slightly but those of C. minutus was little decomposed. The higher tolerance to UVBR of the desert cyanobacterium can be attributed to the higher resistance of its EPS to photodegradation induced by UVBR in comparison with the aquatic species. PMID:27597841

  13. Prevention of graft rejection in allogeneic bone marrow transplantation. II. Preclinical studies with three radiation protocols

    SciTech Connect

    Malilay, G.P.; Sevenich, E.A.; Filipovich, A.H. )

    1990-09-01

    Three radiotherapeutic regimens were compared in vitro to determine their immunosuppressive potential against non-MHC-restricted cytotoxic cells. Assays of natural killer and lymphokine-activated killer function, and cytotoxicity against allogeneic cells were used to quantitate the cytotoxic potential of peripheral blood mononuclear cells from healthy individuals following irradiation with a single dose of 1000 cGy on day 0, 1320 cGy of fractionated radiation (165 cGy b.i.d. x 4 days), or split-dose irradiation consisting of 1000 cGy on day 0 followed 5 or 7 days later by 500 cGy. Both irradiated and nonirradiated (control) PBMC cultures were maintained in culture with medium containing interleukin-2, immunophenotyped, and assayed for cytotoxicity from 1 to 8 days after irradiation. Single dose and fractionated-dose irradiation resulted in a progressive decline in cytotoxic capacity, with an 80% inhibition of both NK and LAK cell activity 8 days after onset of irradiation. The split dose of 500 cGy administered 7 days after a dose of 1000 cGy was found to be the most effective in eliminating NK (93% inhibition) and LAK (100% inhibition) cytotoxicity. These data indicate that split-dose irradiation may result in greater immunosuppression than single-dose or fractionated irradiation.

  14. Temperature-responsiveness and biocompatibility of DEGMA/OEGMA radiation-grafted onto PP and LDPE films

    NASA Astrophysics Data System (ADS)

    Ramírez-Jiménez, Alejandro; Alvarez-Lorenzo, Carmen; Concheiro, Angel; Bucio, Emilio

    2014-06-01

    Polypropylene (PP) and low density polyethylene (LDPE) were modified by γ-ray grafting of di(ethylene glycol) methyl ether methacrylate (DEGMA) and oligo (ethylene glycol) methyl ether methacrylate (OEGMA300 or OEGMA475 with Mn 300 and 475 respectively) with different monomer concentrations and mol ratios. The grafting percentage was evaluated as a function of the solvent, irradiation dose, reaction time, temperature, and monomers concentration. The grafted materials were more hydrophilic than the pristine polymers, as observed by contact angle and swelling in water. Temperature-responsive behavior was evaluated using DSC showing transitions between 34 and 48 °C. In vitro hemocompatibility, protein adsorption, cytotoxicity and bacteria adhesion tests were also carried out. Overall, the DEGMA/OEGMA grafting provides hemo and cytocompatible materials that exhibit temperature-responsive hydrophilic features and decreased protein adsorption.

  15. Effects of Electrons, Protons, and Ultraviolet Radiation on Thermophysical Properties of Polymeric Films

    NASA Technical Reports Server (NTRS)

    Russell, Dennis A.; Connell, John W.; Fogdall, Lawrence B.; Winkler, Werner W.

    2001-01-01

    The response of coated thin polymer films to ultraviolet (UV), electron and proton radiation simultaneously has been evaluated, with selected measurements in situ. Exposure was intended to simulate the electron and proton radiation environment near the Earth-Sun Lagrangian points (LI and L2) for five years and approximately 1000 equivalent solar hours (ESH) UV. These orbital environments are relevant to several potential missions such as the Next Generation Space Telescope and Geomagnetic Storm Warning, both of which may use thin film based structures for a sunshade and solar sail, respectively. The thin film candidates (12.5 micrometers thick) consisted of commercially available materials (Kapton(R) E, HN, Upilex(R) S, CP-1, CP-2, TOR-RC, and TOR-LMBP) that were metalized on one side with vapor deposited aluminum. All of the films are aromatic polyimides, with the exception of TORLMBP, which is a copoly(arylene ether benzimidazole). The films were exposed as second surface mirrors and the effects of the exposure on solar absorptance, thermal emittance, and tensile properties were determined. The in situ changes in solar absorptance from Kapton(R) and Upilex(R) were less than 0. 1, whereas the solar absorptance of TOR and CP films increased by more than 0.3 without saturating. The thermal emittance measurements also showed that the Kapton(R) and Upilex(R) materials increased only 1-2%, but the remaining materials increased 5-8%. Based on tensile property measurements made in air following the test, the failure stress of every type of polymer film decreased as a result of irradiation. The polymers most stable in reflectance, namely Upilex(R) and Kapton(R), were also the strongest in tension before irradiation, and they retained the greatest percentage of tensile strength. The films less stable in reflectance were also weaker in tension, and lost more tensile strength as a result of irradiation. The apparent failure strain (as a percent of original gage length) of

  16. Ethanol production by Kluyveromyces lactis immobilized cells in copolymer carriers produced by radiation polymerization.

    PubMed

    El-Batal, A I; Farahat, L M; El-Rehim, H A

    2000-01-01

    The conditions for batch and continuous production of ethanol, using immobilized growing yeast cells of Kluyveromyces lactis, have been optimized. Yeast cells have been immobilized in hydrogel copolymer carriers composed of polyvinyl alcohol (PVA) with various hydrophilic monomers, using radiation copolymerization technique. Yeast cells were immobilized through adhesion and multiplication of yeast cells themselves. The ethanol production of immobilized growing yeast cells with these hydrogel carriers was related to the monomer composition of the copolymers and the optimum monomer composition was hydroxyethyl methacrylate (HEMA). In this case by using batch fermentation, the superior ethanol production was 32.9 g L(-1) which was about 4 times higher than that of cells in free system. The relation between the activity of immobilized yeast cells and the water content of the copolymer carriers was also discussed. Immobilized growing yeast cells in PVA: HEMA (7%: 10%, w/w) hydrogel copolymer carrier, were used in a packed-bed column reactor for the continuous production of ethanol from lactose at different levels of concentrations (50, 100 and 150) g L(-1). For all lactose feed concentrations, an increase in dilution rates from 0.1 h(-1) to 0.3 h(-1) lowered ethanol concentration in fermented broth, but the volumetric ethanol productivity and volumetric lactose uptake rate were improved. The fermentation efficiency was lowered with the increase in dilution rate and also at higher lactose concentration in feed medium and a maximum of 70.2% was obtained at the lowest lactose concentration 50 g L(-1). PMID:11093678

  17. Polymeric ionic liquid modified graphene oxide-grafted silica for solid-phase extraction to analyze the excretion-dynamics of flavonoids in urine by Box-Behnken statistical design.

    PubMed

    Hou, Xiudan; Liu, Shujuan; Zhou, Panpan; Li, Jin; Liu, Xia; Wang, Licheng; Guo, Yong

    2016-07-22

    A solid-phase extraction method for the efficient analysis of the excretion-dynamics of flavonoids in urine was established and described. In this work, in situ surface radical chain-transfer polymerization and in situ anion exchange were utilized to tune the extraction performance of poly(1-vinyl-3-hexylimidazolium bromide)-graphene oxide-grafted silica (poly(VHIm(+)Br(-))@GO@Sil). Graphene oxide (GO) was first coated onto the silica using a layer-by-layer fabrication method, and then the anion of poly(VHIm(+)Br(-))@GO@Sil was changed into hexafluorophosphate (PF6(-)) by in situ anion exchange. The interaction energies between two PILs and four flavonoids were calculated with the Gaussian09 suite of programs. A Box-Behnken design was used for the optimization of four greatly influential parameters after single-factor experiments to obtain more accurate and precise results. Coupled to high performance liquid chromatography, the poly(VHIm(+)PF6(-))@GO@Sil method showed acceptable extraction recoveries for the four flavonoids, with limits of detection in the range of 0.1-0.5μgL(-1), and wide linear ranges with correlation coefficients (R) ranging from 0.9935 to 0.9987. Under the optimum conditions, the proposed method was applied to analyze the urines collected from a healthy volunteer. The excretion amount-time profiles revealed that 4-15h was the main excretion time for the detected flavonoids. The results indicated that the newly developed method offered the advantages of being feasible, green and cost-effective, and could be successfully applied to the extraction and enrichment of flavonoids in human body systems allowing the study of the metabolic kinetics. PMID:27295963

  18. Polymeric microspheres

    DOEpatents

    Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.

    2004-04-13

    The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

  19. Structural mechanical properties of radiation-sterilized human Bone-Tendon-Bone grafts preserved by different methods.

    PubMed

    Gut, Grzegorz; Marowska, Joanna; Jastrzebska, Anna; Olender, Ewa; Kamiński, Artur

    2016-06-01

    To avoid the risk of infectious disease transmission from donor to recipient, allografts should be terminally sterilized. In the previous paper (Kaminski et al. in Cell Tissue Bank 10:215-219, 2009) we presented the effect of various methods of preservation (deep fresh freezing, glycerolization, lyophilization), followed by irradiation with different doses of electron beam (EB), on material (intrinsic) mechanical properties of human patellar tendons cut out as for anterior cruciate ligament reconstruction, obtained in failure tensile test. As structural mechanical properties are equally important to predict the behaviour of the graft as a whole functional unit, the purpose of the present paper was to show the results for failure load and elongation, obtained in the same experiment. Paired Bone-Tendon-Bone grafts (BTB) were prepared from cadaveric human patella tendons with both patellar and tibial attachments. They were preserved by deep freezing, glycerolization or lyophilization and subsequently EB-irradiated with the doses of 25, 35, 50 or 100 kGy (fresh-frozen grafts) or a single dose of 35 kGy (glycerolized and lyophilized grafts). Each experimental (irradiated) group was provided with control (non-irradiated), donor-matched group. The specimens from all groups were subjected to mechanical failure tensile test with the use of Instron system in order to measure their structural properties (failure load and elongation). All lyophilized grafts were rehydrated before mechanical testing. In our study we did not observe significant deterioration of structural mechanical properties of BTB grafts processed by fresh-freezing and then terminal sterilized with growing doses of EB up to 100 kGy. In contrast, BTB grafts processed by glycerolization or lyophilization and irradiated with 35 kGy showed significant decrease of failure load. Obtained results suggest that deep-frozen irradiated grafts retain their initial mechanical properties to an extent which does not

  20. Role of radiolytically generated species in radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution: Steady state and pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Y. K.; Mohan, H.; Sabharwal, S.; Majali, A. B.

    2000-06-01

    Radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution has been investigated by steady state and pulse radiolysis techniques. Effect of dose, dose rate, monomer concentration, pH and ambient conditions on polymerization was investigated. The reactions of primary radicals of water radiolysis such as OH radical, e -aq, H atom, O rad - and some oxidizing radicals like N rad 3, Cl rad -2,Br rad -2, and reducing specie like CO rad -2 with SSS have also been investigated. SSS reacts with OH radical with a rate constant of 5.9×10 9 dm 3 mol -1s -1 at pH 6.3. The results indicate that ˜83% of OH radicals undergo electron transfer reaction resulting in a cation radical species while remaining ˜17% react via addition reaction. The hydrated electron reacts with SSS with a rate constant 1.3×10 10 dm 3 mol -1 s -1 to form an anion that undergoes fast protonation to form H-adduct at pH 6.3. At high pH (>10) the anion is able to transfer electron to methyl vilogen and p-nitro aceto phenone ( p-NAP) where as H-adduct is unable to transfer electron. At pH ˜1 H atom reaction with SSS is diffusion controlled with a rate constant of 5×10 9 dm 3 mol -1 s -1 and results in formation of H adduct. It was seen that anion reacts with solute an order faster than cation generated radiolytically indicating anionic initiation of polymerization of SSS. Molecular weight of the polymer formed by radiation polymerization, determined by viscosity measurement, are of the order of 10 7 and higher molecular weight polymers are obtained at lower dose rates. In presence of a crosslinking agent gelation of polymer is much faster than the monomer and a polymer concentration ˜20% is most efficiently crosslinked.

  1. Swelling properties of cassava starch grafted with poly (potassium acrylate-co-acrylamide) superabsorbent hydrogel prepared by ionizing radiation

    NASA Astrophysics Data System (ADS)

    Barleany, Dhena Ria; Ulfiyani, Fida; Istiqomah, Shafina; Heriyanto, Heri; Rahmayetty, Erizal

    2015-12-01

    Natural and synthetic hydrophylic polymers can be phisically or chemically cross-linked in order to produce hydrogels. Starch based hydrogels grafted with copolymers from acrylic acid or acrylamide have become very popular for water absorbent application. Superabsorbent hydrogels made from Cassava starch grafted with poly (potassium acrylate-co-acrylamide) were prepared by using of ϒ-irradiation method. Various important parameters such as irradiation doses, monomer to Cassava starch ratio and acrylamide content were investigated. The addition of 7,5 % w w-1 acrylamide into the reaction mixture generated a starch graft copolymer with a water absorption in distilled water as high as 460 g g-1 of its dried weight. The effectivity of hydrogel as superabsorbent for aqueous solutions of NaCl and urea was evaluated. The obtained hydrogel showed the maximum absorptions of 317 g g-1 and 523 g g-1 for NaCl and urea solution, respectively (relative to its own dry weight). The structure of the graft copolymer was analyzed by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM).

  2. Swelling properties of cassava starch grafted with poly (potassium acrylate-co-acrylamide) superabsorbent hydrogel prepared by ionizing radiation

    SciTech Connect

    Barleany, Dhena Ria Ulfiyani, Fida; Istiqomah, Shafina; Rahmayetty; Heriyanto, Heri; Erizal

    2015-12-29

    Natural and synthetic hydrophylic polymers can be phisically or chemically cross-linked in order to produce hydrogels. Starch based hydrogels grafted with copolymers from acrylic acid or acrylamide have become very popular for water absorbent application. Superabsorbent hydrogels made from Cassava starch grafted with poly (potassium acrylate-co-acrylamide) were prepared by using of ϒ-irradiation method. Various important parameters such as irradiation doses, monomer to Cassava starch ratio and acrylamide content were investigated. The addition of 7,5 % w w{sup −1} acrylamide into the reaction mixture generated a starch graft copolymer with a water absorption in distilled water as high as 460 g g{sup −1} of its dried weight. The effectivity of hydrogel as superabsorbent for aqueous solutions of NaCl and urea was evaluated. The obtained hydrogel showed the maximum absorptions of 317 g g{sup −1} and 523 g g{sup −1} for NaCl and urea solution, respectively (relative to its own dry weight). The structure of the graft copolymer was analyzed by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM)

  3. Photoacid-mediated ring opening polymerization driven by visible light.

    PubMed

    Fu, Changkui; Xu, Jiangtao; Boyer, Cyrille

    2016-06-01

    A novel methodology of visible light regulated ring opening polymerization in the presence of reversible merocyanine-based photoacid was reported for the first time. In combination with a photoinduced radical polymerization technique, a dual wavelength light controlled orthogonal polymerization system was investigated to switch the polymerization between two different monomers and for the preparation of block and graft copolymers in one pot. PMID:27167862

  4. Physical properties of agave cellulose graft polymethyl methacrylate

    NASA Astrophysics Data System (ADS)

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan

    2013-11-01

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm-1 which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  5. Physical properties of agave cellulose graft polymethyl methacrylate

    SciTech Connect

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan

    2013-11-27

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm{sup −1} which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  6. Uranium Recovery from Seawater: Development of Fiber Adsorbents Prepared via Atom-Transfer Radical Polymerization

    SciTech Connect

    Saito, Tomonori; Brown, Suree; Chatterjee, Sabornie; Kim, Jungseung; Tsouris, Costas; Mayes, Richard T; Kuo, Li-Jung; Gill, Gary; Oyola, Yatsandra; Janke, Christopher James; Dai, Sheng

    2014-01-01

    A novel adsorbent preparation method using atom-transfer radical polymerization (ATRP) combined with radiation-induced graft polymerization (RIGP) was developed to synthesize an adsorbent for uranium recovery from seawater. The ATRP method allowed a much higher degree of grafting on the adsorbent fibers (595 2818%) than that allowed by RIGP alone. The adsorbents were prepared with varied composition of amidoxime groups and hydrophilic acrylate groups. The successful preparation revealed that both ligand density and hydrophilicity were critical for optimal performance of the adsorbents. Adsorbents synthesized in this study showed a relatively high performance (141 179 mg/g at 49 62 % adsorption) in laboratory screening tests using a uranium concentration of ~6 ppm. This performance is much higher than that of known commercial adsorbents. However, actual seawater experiment showed impeded performance compared to the recently reported high-surface-area-fiber adsorbents, due to slow adsorption kinetics. The impeded performance motivated an investigation of the effect of hydrophilic block addition on the graft chain terminus. The addition of hydrophilic block on the graft chain terminus nearly doubled the uranium adsorption capacity in seawater, from 1.56 mg/g to 3.02 mg/g. The investigation revealed the importance of polymer chain conformation, in addition to ligand and hydrophilic group ratio, for advanced adsorbent synthesis for uranium recovery from seawater.

  7. Synthesis and characterization of radiation grafted films for removal of arsenic and some heavy metals from contaminated water

    NASA Astrophysics Data System (ADS)

    Chowdhury, M. N. K.; Khan, M. W.; Mina, M. F.; Beg, M. D. H.; Khan, Maksudur R.; Alam, A. K. M. M.

    2012-10-01

    Grafting of styrene/maleic anhydride and methyl methacrylate/maleic anhydride binary monomers onto the low density polyethylene film was performed using the γ-ray irradiation technique. Then, the synthesized grafted films were treated with different ammonia derivatives for developing chelating functionalization. These chelating products were characterized by the gravimetric method as well as by the Fourier transformed infrared spectroscopic method, and were used for removal of arsenic and some heavy metals from aqueous solutions. The optimum absorbed dose of 30 kGy reveals the graft yielding of about 325% in the films. Uptake of arsenic and some heavy-metal ions (Cr(III), Mn(II), Fe(III), Ni(II), Cu(II) and Pb(II)) from contaminated water by the chelating functionalized films (CFF) was examined by an atomic absorption spectrophotometer. The maximum arsenic removal capacity of 5062 mg/kg has been observed for the film treated with hydroxylamine hydrochloride. The CFF prepared by semicarbazide and thiol analogs show affinity toward the metal ions with an order: Cu(II)>Fe(III)>Mn(II) etc. The results obtained from this study indicate that the functionalized films show good chelating and ion-exchange property for metal ions.

  8. Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

    PubMed

    Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

    2011-05-21

    In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles

  9. Flexible particle array structures by controlling polymer graft architecture.

    PubMed

    Choi, Jihoon; Dong, Hongchen; Matyjaszewski, Krzysztof; Bockstaller, Michael R

    2010-09-15

    Surface-initiated atom-transfer radical polymerization is used to synthesize particle brushes with controlled fraction of extended and relaxed conformations of surface-grafted chains. In the semidilute brush limit, the grafting of polymeric ligands is shown to facilitate the formation of ordered yet plastic-compliant particle array structures in which chain entanglements give rise to fracture through a polymer-like crazing process that dramatically increases the toughness and flexibility of the particle assembly. PMID:20726581

  10. Antimicrobial Graft Copolymer Gels.

    PubMed

    Harvey, Amanda C; Madsen, Jeppe; Douglas, C W Ian; MacNeil, Sheila; Armes, Steven P

    2016-08-01

    In view of the growing worldwide rise in microbial resistance, there is considerable interest in designing new antimicrobial copolymers. The aim of the current study was to investigate the relationship between antimicrobial activity and copolymer composition/architecture to gain a better understanding of their mechanism of action. Specifically, the antibacterial activity of several copolymers based on 2-(methacryloyloxy)ethyl phosphorylcholine [MPC] and 2-hydroxypropyl methacrylate (HPMA) toward Staphylococcus aureus was examined. Both block and graft copolymers were synthesized using either atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization and characterized via (1)H NMR, gel permeation chromatography, rheology, and surface tensiometry. Antimicrobial activity was assessed using a range of well-known assays, including direct contact, live/dead staining, and the release of lactate dehydrogenase (LDH), while transmission electron microscopy was used to study the morphology of the bacteria before and after the addition of various copolymers. As expected, PMPC homopolymer was biocompatible but possessed no discernible antimicrobial activity. PMPC-based graft copolymers comprising PHPMA side chains (i.e. PMPC-g-PHPMA) significantly reduced both bacterial growth and viability. In contrast, a PMPC-PHPMA diblock copolymer comprising a PMPC stabilizer block and a hydrophobic core-forming PHPMA block did not exhibit any antimicrobial activity, although it did form a biocompatible worm gel. Surface tensiometry studies and LDH release assays suggest that the PMPC-g-PHPMA graft copolymer exhibits surfactant-like activity. Thus, the observed antimicrobial activity is likely to be the result of the weakly hydrophobic PHPMA chains penetrating (and hence rupturing) the bacterial membrane. PMID:27409712

  11. Bone Grafts

    MedlinePlus

    ... repair and rebuild diseased bones in your hips, knees, spine, and sometimes other bones and joints. Grafts can also repair bone loss caused by some types of fractures or cancers. Once your body accepts the bone ...

  12. Synthesis and characterization of superabsorbent polymer prepared by radiation-induced graft copolymerization of acrylamide onto carboxymethyl cellulose for controlled release of agrochemicals

    NASA Astrophysics Data System (ADS)

    Hemvichian, Kasinee; Chanthawong, Auraruk; Suwanmala, Phiriyatorn

    2014-10-01

    Superabsorbent polymer (SAP) was synthesized by radiation-induced grafting of acrylamide (AM) onto carboxymethyl cellulose (CMC) in the presence of a crosslinking agent, N,N‧-methylenebisacrylamide (MBA). The effects of various parameters, such as dose, the amount of CMC, AM, MBA and ionic strength on the swelling ratio were investigated. In order to evaluate its controlled release potential, SAP was loaded with potassium nitrate (KNO3) as an agrochemical model and its potential for controlled release of KNO3 was studied. The amount of released KNO3 was analyzed by an inductively coupled plasma mass spectrometry (ICP-MS). The results from controlled release experiment agreed very well with the results from swelling experiment. The synthesized SAP was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The obtained SAP exhibited a swelling ratio of 190 g/g of dry gel.

  13. Grafting chitosan and polyHEMA on carbon nanotubes surfaces: "grafting to" and "grafting from" methods.

    PubMed

    Mahmoodian, Hossein; Moradi, Omid; Shariatzadeh, Behnam

    2014-02-01

    We report a simple method for engineering chitosan (CS) functionalized multi-walled carbon nanotube (MWCNT) composites with a biomedically important polymer, poly-2-hydroxyethyl methacrylate (polyHEMA), by chemical grafting HEMA monomers via free radical polymerization. Functionalization of CS and polyHEMA occurred in three steps. First, using microwave irradiation, CS was grafted onto the surface and sidewall of the carbon nanotubes. Second, HEMA monomers were grafted onto the polymeric matrix surface. The final step involved free radical polymerization of HEMA monomers. Composite synthesis was confirmed by Fourier transform infrared (FTIR) spectroscopy. Moreover, the presence of polyHEMA on the surface of the CS functionalized carbon nanotubes was confirmed by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and thermo gravimetric analysis (TGA) analyses. Furthermore, in the aqueous phase, our novel composites exhibited higher dispersibility compared with pristine MWCNTs. Considering the biomedical importance of polyHEMA and CS polymers, we expect these materials to be useful in the pharmaceutical industry as novel biomaterial composites with potential applications in drug delivery. PMID:24183808

  14. Impact of reaction conditions on grafting acrylamide onto starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have explored the radical initiated graft polymerization reaction of acrylamide onto starch where the solvent, concentration, temperature and reaction times were varied. We have found that the morphology of the resulting grafted polymer is dramatically different and is dependent on the reaction c...

  15. Production of monodisperse, polymeric microspheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chang, Manchium (Inventor)

    1990-01-01

    Very small, individual polymeric microspheres with very precise size and a wide variation in monomer type and properties are produced by deploying a precisely formed liquid monomer droplet, suitably an acrylic compound such as hydroxyethyl methacrylate into a containerless environment. The droplet which assumes a spheroid shape is subjected to polymerizing radiation such as ultraviolet or gamma radiation as it travels through the environment. Polymeric microspheres having precise diameters varying no more than plus or minus 5 percent from an average size are recovered. Many types of fillers including magnetic fillers may be dispersed in the liquid droplet.

  16. Synthesis of arsenic graft adsorbents in pilot scale

    NASA Astrophysics Data System (ADS)

    Hoshina, Hiroyuki; Kasai, Noboru; Shibata, Takuya; Aketagawa, Yasushi; Takahashi, Makikatsu; Yoshii, Akihiro; Tsunoda, Yasuhiko; Seko, Noriaki

    2012-08-01

    Synthesis of arsenic (As) adsorbents in pilot scale was carried out with a synthesizing apparatus by radiation-induced graft polymerization of 2-hydroxyethyl methacrylate phosphoric acid monomer (PA), which consists of phosphoric acid mono- (50%) and di- (50%) ethyl methacrylate esters onto a nonwoven cotton fabric (NCF), and following chemical modification by contact with a zirconium (Zr) solution. The apparatus which was equipped with reaction tanks, a washing tank and a pump can produce up to 0.3 m×14 m size of the As(V) adsorbent in one reaction. A degree of grafting of 150% was obtained at an irradiation dose of 20 kGy with 5% of PA solution mixed with deionized water for 1 h at 40 °C. Finally, after Zr(IV) was loaded onto a NCF with 5 mmol/L of Zr(IV) solution, the graft adsorbent for the removal of As(V) was achieved in pilot-scale. The adsorbent which was synthesized in pilot scale was evaluated in batch mode adsorption with 1 ppm (mg/l) of As(V) solution for 2 h at room temperature. As a result, the adsorption capacity for As(V) was 0.02 mmol/g-adsorbent.

  17. Radiation and photografting as complementary techniques for immobilizing bioactive materials

    NASA Astrophysics Data System (ADS)

    Garnett, J. L.; Jankiewicz, S. V.; Long, M. A.; Sangster, D. F.

    The technique of radiation grafting to immobilize a typical enzyme, trypsin, to three representative backbone polymers namely polypropylene, PVC and polystyrene, is described. The process involves the simultaneous grafting of p-nitrostyrene to the polymer, the nitro group subsequently being converted to its isothiocyanato derivative to which trypsin is attached. For this immobilization work, the utilization of additives which enhance grafting is shown to be an advantage. Typical of the additives used are mineral acids (≈0.1M) and polyfunctional monomers (≈1% v/v), the two acting in a synergistic fashion when used together. A new class of additives, namely metal salts such as LiClO 4, which also increase grafting yields has now been discovered. The reactivity of these salts in grafting enhancement is compared with that of mineral acid. A new model for the modus operandi of metal salts as well as acids in grafting enhancement is proposed whereby increased grafting yields are attributed to increased partitioning of monomer into the graft region in the presence of ionic solutes. The significance of using these additives to prepare radiation copolymers for enzyme immobilization is discussed. In addition to ionizing radiation, UV is also shown to be of value as an initiator for the preparation of graft copolymers for enzyme immobilization, however the presence of sensitizer in the copolymer may limit the photografting method. The possibility of using radiation curing processes involving electron beam (EB) and high powered (300 W/inch) UV sources for immobilization work has been explored and found to be feasible. The curing system possesses great potential for the current immobilization work since complete polymerization is achieved in a fraction of a second.

  18. Structure-function properties of starch graft poly(methyl acrylate)copolymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spherulites, produced by steam jet-cooking high-amylose starch and oleic acid, were grafted with methyl acrylate, both before and after removal of un-complexed amylopectin. For comparison, granular high-amylose corn starch was graft polymerized in a similar manner. The amount of grafted and ungrafte...

  19. Structure-function properties of starch spherulites grafted with poly(methyl acrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spherulites, produced by steam jet-cooking high-amylose starch and oleic acid, were grafted with methyl acrylate, both before and after removal of un-complexed amylopectin. For comparison, granular high-amylose corn starch was graft polymerized in a similar manner. The amount of grafted and ungrafte...

  20. Polymerization catalyst

    SciTech Connect

    Graves, V.

    1987-05-12

    A process is described for polymerizing at least one alpha olefin under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of a catalyst system which comprises: a supported catalyst prepared under anhydrous conditions by the sequential steps of: preparing a slurry of inert particulate support material; adding to the slurry a solution of an organomagnesium compound; adding to the slurry and reacting a solution of a zirconium halide compound, hafnium compound or mixtures thereof; adding to the slurry and reacting a halogenator; adding to the slurry and reacting a tetravalent titanium halide compound; and recovering solid catalyst.

  1. Polymerization catalyst

    SciTech Connect

    Graves, V.

    1986-10-21

    A process is described for polymerizing at least one alpha-olefin under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of a catalyst comprising: a supported catalyst prepared under anhydrous conditions by the steps of: (1) sequentially; (a) preparing a slurry of inert particulate support material; (b) adding to the slurry a solution of an organomagnesium compound; (c) adding to the slurry and reacting a solution of zirconium compound; and (2) thereafter; (d) adding to the slurry and reacting a halogenator; (e) adding to the slurry and reacting a tetravalent titanium compound; (f) recovering solid catalyst; and an organoaluminum compound.

  2. Polymerization and surface modification by low pressure plasma technique

    NASA Astrophysics Data System (ADS)

    Tsafack, M.-J.; Hochart, F.; Levalois-Grützmacher, J.

    2004-06-01

    A durable water repellent, stain resistant or flame retardant character can be conferred to polyacrylonitrile (PAN) textiles by using the plasma induced graft polymerization technique. The monomers used are perfluoroalkylacrylate, (meth)acrylate phosphates, and phosphonates which are well known to be effective for the waterproofing and the fireproofing of polymeric substrates, respectively.

  3. Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization from Chlorinated Polypropylene and Polyethylene Trunk Fibers

    DOE PAGESBeta

    Brown, Suree; Chatterjee, Sabornie; Li, Meijun; Yue, Yanfeng; Tsouris, Costas; Janke, Christopher J.; Saito, Tomonori; Dai, Sheng

    2015-12-10

    Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers wasmore » prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.« less

  4. Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization from Chlorinated Polypropylene and Polyethylene Trunk Fibers

    SciTech Connect

    Brown, Suree; Chatterjee, Sabornie; Li, Meijun; Yue, Yanfeng; Tsouris, Costas; Janke, Christopher J.; Saito, Tomonori; Dai, Sheng

    2015-12-10

    Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers was prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.

  5. Laundering durable antibacterial cotton fabrics grafted with pomegranate-shaped polymer wrapped in silver nanoparticle aggregations

    NASA Astrophysics Data System (ADS)

    Liu, Hanzhou; Lv, Ming; Deng, Bo; Li, Jingye; Yu, Ming; Huang, Qing; Fan, Chunhai

    2014-08-01

    To improve the laundering durability of the silver functionalized antibacterial cotton fabrics, a radiation-induced coincident reduction and graft polymerization is reported herein where a pomegranate-shaped silver nanoparticle aggregations up to 500 nm can be formed due to the coordination forces between amino group and silver and the wrapping procedure originated from the coincident growth of the silver nanoparticles and polymer graft chains. This pomegranate-shaped silver NPAs functionalized cotton fabric exhibits outstanding antibacterial activities and also excellent laundering durability, where it can inactivate higher than 90% of both E. coli and S. aureus even after 50 accelerated laundering cycles, which is equivalent to 250 commercial or domestic laundering cycles.

  6. Effects of high energy simulated space radiation on polymeric second-surface mirrors. [thermal control coatings - performance tests

    NASA Technical Reports Server (NTRS)

    Eogdall, L. B.; Cannaday, S. S.

    1975-01-01

    A radiation effects experimental program was performed, in which second surface mirror type thermal control coatings were exposed to ultraviolet radiation, electrons, and protons simultaneously. Stability was assessed by making periodic spectral reflectance measurements in situ (and in air after testing for comparison). Solar absorption coefficients were derived by computer. Many of the exposed materials showed large amounts of degradation in reflectance absorptance, principally due to the electron exposure. A series of tests was conducted, leading to the identification of a modified second surface mirror that shows considerable improvement and promise for stability during thermal control applications in a charged particle space radiation environment.

  7. Graft copolymers from poly(2,6-dimethylphenylene oxide) and pivalolactone

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L.; Wakelyn, N. T.

    1988-01-01

    The copolyether-polyester system resulting from the anionic graft polymerization of pivalolactone onto poly(2,6-dimethylphenylene oxide) has been formulated with differing graft densities and graft segment lengths. Wide angle X-ray scattering studies on these materials indicated an increased crystalline order with increased PVL segments/graft for similarly annealed specimens and a decrease in such order with increasing carboxylation.

  8. Polymeric nanoparticles

    PubMed Central

    Bolhassani, Azam; Javanzad, Shabnam; Saleh, Tayebeh; Hashemi, Mehrdad; Aghasadeghi, Mohammad Reza; Sadat, Seyed Mehdi

    2014-01-01

    Nanocarriers with various compositions and biological properties have been extensively applied for in vitro/in vivo drug and gene delivery. The family of nanocarriers includes polymeric nanoparticles, lipid-based carriers (liposomes/micelles), dendrimers, carbon nanotubes, and gold nanoparticles (nanoshells/nanocages). Among different delivery systems, polymeric carriers have several properties such as: easy to synthesize, inexpensive, biocompatible, biodegradable, non-immunogenic, non-toxic, and water soluble. In addition, cationic polymers seem to produce more stable complexes led to a more protection during cellular trafficking than cationic lipids. Nanoparticles often show significant adjuvant effects in vaccine delivery since they may be easily taken up by antigen presenting cells (APCs). Natural polymers such as polysaccharides and synthetic polymers have demonstrated great potential to form vaccine nanoparticles. The development of new adjuvants or delivery systems for DNA and protein immunization is an expanding research field. This review describes polymeric carriers especially PLGA, chitosan, and PEI as vaccine delivery systems. PMID:24128651

  9. Clinical factors increasing radiation doses to patients undergoing long-lasting procedures: Abdominal stent-graft implantation

    PubMed Central

    Majewska, Natalia; Stanisic, Michal G.; Blaszak, Magdalena Aleksandra; Juszkat, Robert; Frankiewicz, Maciej; Krasinski, Zbigniew; Makalowski, Marcin; Majewski, Waclaw

    2011-01-01

    Summary Background An important negative factor of EVAR is the radiation acquired during long-lasting procedures. The aim of the study was to document the radiation doses of EVAR and to discuss potential reasons for prolongation of radiological procedures. Material/Methods Dose-area product (DAP) (Gy cm2) and air kerma (AK) (Gy) obtained during EVAR from 92 patients were analyzed retrospectively in regards to body mass index (BMI), angulations of aneurysm neck, length of aneurysm neck and occurrence of tortuosity of iliac arteries. Results Total AK for fluoroscopy differed significantly between normal BMI (373 mGy) and BMI 25–29.9 (1125 mGy) or BMI >30 (1085 mGy). Iliac artery tortuosities >45° and short aneurysm necks caused higher doses of total AK (1097 mGy and 1228 mGy, respectively) than iliac artery tortuosities <45° and long aneurysm necks (605 mGy and 720 mGy, respectively). Conclusions The main factors contributing to a high radiation dose being acquired by patients during EVAR are: BMI >25, tortuosity of iliac arteries >45° and short aneurysm necks. PMID:22037751

  10. Chronic graft-versus-host disease in the rat radiation chimera: I. clinical features, hematology, histology, and immunopathology in long-term chimeras

    SciTech Connect

    Beschorner, W.E.; Tutschka, P.J.; Santos, G.W.

    1982-04-01

    The clinical features, pathology, and immunopathology of chronic graft-versus-host disease (GVHD) developing in the long-term rat radiation chimera are described. At 6 to 12 months post-transplant, the previously stable ACI/LEW chimeras developed patchy to diffuse severe hair loss and thickened skin folds, and had microscopic features resembling scleroderma, Sjogren's syndrome, and chronic hepatitis. Skin histology showed dermal inflammation and acanthosis with atrophy of the appendages, with progression to dermal sclerosis. The liver revealed chronic hepatitis with bile duct injury and proliferation and periportal piecemeal necrosis. The tongue had considerable submucosal inflammation, muscular necrosis, and atrophy and arteritis. The serous salivary glands, lacrimal glands, and bronchi had lymphocytic inflammation and injury to duct, acinar, and mucosal columnar epithelium. The thymus had lymphocyte depletion of the medulla with prominent epithelium. The spleen and lymph nodes had poorly developed germinal centers but increased numbers of plasma cells. IgM was observed along the basement membrane and around the basal cells of the skin and tongue and along the basement membrane of the bile ducts. IgM was present also in the arteries of the tongue. Immunoglobulins eluted from the skin, cross-reacted with the bile duct epithelium and usually with both ACI and Lewis skin. Increased titers of speckled antinuclear antibodies were present in the serum of rats with chronic (GVHD). Chronic GVHD in the long-term rat radiation chimera is very similar to human chronic GVHD and is a potentially excellent model for autoimmune disorders including scleroderma, Sjorgren's syndrome, and chronic hepatitis.

  11. Therapeutic Potential of Gingival Fibroblasts for Cutaneous Radiation Syndrome: Comparison to Bone Marrow-Mesenchymal Stem Cell Grafts

    PubMed Central

    Tissedre, Frederique; Busson, Elodie; Holler, Valerie; Leclerc, Thomas; Strup-Perrot, Carine; Couty, Ludovic; L'homme, Bruno; Benderitter, Marc; Lafont, Antoine; Lataillade, Jean Jacques; Coulomb, Bernard

    2015-01-01

    Mesenchymal stem cell (MSC) therapy has recently been investigated as a potential treatment for cutaneous radiation burns. We tested the hypothesis that injection of local gingival fibroblasts (GFs) would promote healing of radiation burn lesions and compared results with those for MSC transplantation. Human clinical- grade GFs or bone marrow-derived MSCs were intradermally injected into mice 21 days after local leg irradiation. Immunostaining and real-time PCR analysis were used to assess the effects of each treatment on extracellular matrix remodeling and inflammation in skin on days 28 and 50 postirradiation. GFs induced the early development of thick, fully regenerated epidermis, skin appendages, and hair follicles, earlier than MSCs did. The acceleration of wound healing by GFs involved rearrangement of the deposited collagen, modification of the Col/MMP/TIMP balance, and modulation of the expression and localization of tenascin-C and of the expression of growth factors (VEGF, EGF, and FGF7). As MSC treatment did, GF injection decreased the irradiation-induced inflammatory response and switched the differentiation of macrophages toward an M2-like phenotype, characterized by CD163+ macrophage infiltration and strong expression of arginase-1. These findings indicate that GFs are an attractive target for regenerative medicine, for easier to collect, can grow in culture, and promote cutaneous wound healing in irradiation burn lesions. PMID:25584741

  12. Structure-function properties of amylose-oleic acid inclusion complexes grafted with poly(methyl acrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spherulites, produced by steam jet-cooking high-amylose starch and oleic acid, were grafted with methyl acrylate, both before and after removal of un-complexed amylopectin. For comparison, granular high-amylose corn starch was graft polymerized in a similar manner. The amount of grafted and ungrafte...

  13. Radiation grafting of pH-sensitive acrylic acid and 4-vinyl pyridine onto nylon-6 using one- and two-step methods

    NASA Astrophysics Data System (ADS)

    Ortega, Alejandra; Alarcón, Darío; Muñoz-Muñoz, Franklin; Garzón-Fontecha, Angélica; Burillo, Guillermina

    2015-04-01

    Acrylic acid (AAc) and 4-vinyl pyridine (4VP) were γ-ray grafted onto nylon-6 (Ny6) films via pre-irradiation oxidative method. These monomers were grafted using a one-step method to render Ny6-g-(AAc/4VP). A two-step or sequential method was used to render (Ny6-g-AAc)-g-4VP. Random copolymer branches were obtained when the grafting was carried out via one-step method using the two monomers together. The two-step method was applied to graft chains of 4VP on both Ny6 substrate and previously grafted AAc chains (Ny6-g-AAc). The two types of binary copolymers synthesized were characterized to determine the amount of grafted polymers, the thermal behavior (DSC and TGA), the surface composition (XPS), and the pH responsiveness. In the two-step process, it is possible to achieve a higher graft yield, better control of the amount of each monomer, good reversibility in the swelling/deswelling process and shorter time to achieve equilibrium swelling.

  14. Preparation and characterization of Fe(III)-loaded iminodiacetic acid modified GMA grafted nonwoven fabric adsorbent for anion adsorption

    NASA Astrophysics Data System (ADS)

    Kavaklı, Pınar Akkaş; Kavaklı, Cengiz; Güven, Olgun

    2014-01-01

    An Fe(III)-loaded chelating fabric with iminodiacetic acid (IDA) functional groups was prepared by radiation induced graft polymerization of an epoxy group containing monomer, glycidyl methacrylate, onto a nonwoven fabric made of polypropylene coated by polyethylene (PE/PP) and subsequent Fe(III) loading. Grafting conditions were optimized, and GMA grafted polymer was modified with iminodiacetic acid in isopropyl alcohol/water at 80 °C. In order to prepare the polymeric ligand exchanger (PLE) for the removal of phosphate, IDA fabrics were loaded with Fe(III) ions. Fe(III) loading capacity of IDA fabric was determined to be 2.83 mmol Fe(III)/g of polymer. For removal of phosphate anion, adsorption experiments were performed in batch mode at different pH (2-9) and phosphate concentrations. It was found that phosphate adsorption by the Fe(III)-loaded IDA fabric is maximum at pH 2.00. The effect of initial concentration of phosphate on the adsorption behaviour of Fe(III)-loaded IDA nonwoven fabric was determined at low phosphate concentrations (0.5-25 ppm) and at high phosphate concentrations (50-1000 ppm).

  15. Chain Reaction Polymerization.

    ERIC Educational Resources Information Center

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

  16. Surface-initiated atom transfer radical polymerization from chitin nanofiber macroinitiator film.

    PubMed

    Yamamoto, Kazuya; Yoshida, Sho; Kadokawa, Jun-Ichi

    2014-11-01

    This paper reports the preparation of chitin nanofiber-graft-poly(2-hydroxyethyl acrylate) (CNF-g-polyHEA) films by surface-initiated atom transfer radical polymerization (ATRP) of HEA monomer from a CNF macroinitiator film. First, a CNF film was prepared by regeneration from a chitin ion gel with an ionic liquid. Then, acylation of the CNF surface with α-bromoisobutyryl bromide was carried out to obtain the CNF macroinitiator film having the initiating moieties (α-bromoisobutyrate group). The surface-initiated graft polymerization of HEA from the CNF macroinitiator film by ATRP was performed to produce the CNF-g-polyHEA film. The IR, XRD, and SEM measurements of the resulting film indicated the progress of the graft polymerization of HEA on surface of CNFs. The molecular weights of the grafted polyHEAs increased with prolonged polymerization times, which affected the mechanical properties of the films under tensile mode. PMID:25129725

  17. Hemoglobin loaded polymeric nanoparticles: preparation and characterizations.

    PubMed

    Dessy, Alberto; Piras, Anna M; Schirò, Giorgio; Levantino, Matteo; Cupane, Antonio; Chiellini, Federica

    2011-05-18

    In the present work polymeric nanoparticles based on Poly (maleic anhydride-alt-butyl vinyl ether) 5% grafted with m-PEG (2000) and 95% grafted with 2-methoxyethanol (VAM41-PEG) were loaded with human hemoglobin (Hb) and characterized from a physicochemical point of view. The assessment of structural and functional features of the loaded Hb was performed and the effect of the introduction of different reducing agents as aimed at minimizing Hb oxidation during the nanoparticles formulation process, was also investigated. Nanoparticles possessing an average diameter of 138±10 nm and physicochemical features suitable for this kind of application were successfully obtained. Although the oxidation of the protein was not avoided during its loading into nanoparticles, the presence of acidic moieties in the polymeric structure is proposed to be directly involved in the protein inactivation mechanism. PMID:21443949

  18. Electrostrictive Graft Elastomers

    NASA Technical Reports Server (NTRS)

    Su, Ji (Inventor); Harrison, Joycelyn S. (Inventor); St.Clair, Terry L. (Inventor)

    2003-01-01

    An electrostrictive graft elastomer has a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules. The polar graft moieties have been rotated by an applied electric field, e.g., into substantial polar alignment. The rotation is sustained until the electric field is removed. In another embodiment, a process for producing strain in an elastomer includes: (a) providing a graft elastomer having a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules; and (b) applying an electric field to the graft elastomer to rotate the polar graft moieties, e.g., into substantial polar alignment.

  19. Two Photon Polymerization of Ormosils

    NASA Astrophysics Data System (ADS)

    Matei, A.; Zamfirescu, M.; Jipa, F.; Luculescu, C.; Dinescu, M.; Buruiana, E. C.; Buruiana, T.; Sima, L. E.; Petrescu, S. M.

    2010-10-01

    In this work, 3D structures of hybrid polymers—ORMOSILS (organically modified silicates) were produced via Two Photon Polymerization (2PP) of hybrid methacrylates based on silane derivates. Synthetic routes have been used to obtain series of hybrid monomers, their structure and purity being checked by NMR Spectroscopy and Fourier Transform Infrared Spectroscopy. Two photon polymerization method (a relatively new technology which allows fast micro and nano processing of three-dimensional structures with application in medical devices, tissue scaffolds, photonic crystals etc) was used for monomers processing. As laser a Ti: Sapphire laser was used, with 200 fs pulse duration and 2 kHz repetition rate, emitting at 775 nm. A parametric study on the influence of the processing parameters (laser fluence, laser scanning velocity, photo initiator) on the written structures was carried out. The as prepared polymeric scaffolds were tested in mesenchymal stem cells and fibroblasts cell cultures, with the aim of further obtaining bone and dermal grafts. Cells morphology, proliferation, adhesion and alignment were analyzed for different experimental conditions.

  20. Immobilization of Polymeric Luminophor on Nanoparticles Surface

    NASA Astrophysics Data System (ADS)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-04-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor.

  1. Grafting of oligosaccharides onto synthetic polymer colloids.

    PubMed

    Mange, Siyabonga; Dever, Cédric; De Bruyn, Hank; Gaborieau, Marianne; Castignolles, Patrice; Gilbert, Robert G

    2007-06-01

    A new method to form colloidally stable oligosaccharide-grafted synthetic polymer particles has been developed. The oligosaccharides, of weight-average degree of polymerization approximately 38, were obtained by enzymatic debranching of amylopectin. Through the use of a cerium(IV)-based redox initiation process, oligosaccharide chains are grafted onto a synthetic polymer colloid comprising electrostatically stabilized poly(methyl methacrylate) or polystyrene latex particles swollen with methyl methacrylate monomer. Ce(IV) creates a radical species on these oligosaccharides, which then propagates, initially with aqueous-phase monomer, then with the methyl methacrylate monomer inside the particles. Ultracentrifugation, NMR, and total starch analyses together prove that the grafting process has occurred, with at least 7.7 wt % starch grafted and a grafting efficiency of 33%. The surfactant used in latex preparation was removed by dialysis, resulting in particles colloidally stabilized with only linear starch as a steric stabilizer. The debranched starch that comprises these oligosaccharides is found to be a remarkably effective colloidal stabilizer, albeit at low electrolyte concentration, stabilizing particles with very sparse surface coverage. PMID:17497920

  2. Bone grafts in dentistry

    PubMed Central

    Kumar, Prasanna; Vinitha, Belliappa; Fathima, Ghousia

    2013-01-01

    Bone grafts are used as a filler and scaffold to facilitate bone formation and promote wound healing. These grafts are bioresorbable and have no antigen-antibody reaction. These bone grafts act as a mineral reservoir which induces new bone formation. PMID:23946565

  3. Synthesis and characterization of carbon fibers functionalized with poly (glycidyl methacrylate) via atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Wu, Yongwei; Xiong, Lei; Qin, Xiaokang; Wang, Zhengyue; Ding, Bei; Ren, Huan; Pi, Xiaolong

    2015-07-01

    In this work, polyacrylonitrile (PAN)-based carbon fibers (CF) were chemically modified with poly (glycidyl methacrylate) (PGMA) via atom transfer radical polymerization (ATRP) to improve the interaction between the CF and polymer matrix. The FT-IR, TGA, and XPS were used to determine the chemical structure of the resulting products and the quantities of PGMA chains grafted from the CF surface. The experimental results confirm that the CF surface was functionalized and glycidyl methacrylate was graft-polymerized onto the CF, and the grafting content of polymer could reach 10.2%.

  4. Effect of the nature of the components of extraction systems used to extract radionuclides on interfacial tension. V. Radiation polymerization products of tri-n-butyl phosphate

    SciTech Connect

    Nikitin, S.D.; Shmidt, V.S.

    1986-01-01

    This paper examines the effect of the polymerization products of tri-n-butylphosphate (TBP) on stratification of normal and inverse emulsions and the interfacial tension in systems of 30% TBP in n-dodecane with water, 5% aqueous solution Na/sub 2/CO/sub 3/, and a solution of 3 moles/liter HNO/sub 3/. It is shown that in these systems there is a direct correlation between the interfacial tension and the phase stratification rate. Small additions of a neutral fraction of the polymerization products do not exert any appreciable effect on the interfacial tension and the phase stratification rate in the investigated systems.

  5. Polymerization of perfluorobutadiene at near-ambient conditions

    NASA Technical Reports Server (NTRS)

    Toy, M. S.

    1971-01-01

    Peroxide catalyst under mild conditions initiates homopolymerization of perfluoro butadiene to new linear perfluoro polyenes and vulcanizable fluoro elastomers. Resulting polyperfluoro butadiene serves as hard elastomer for good chemical resistance, as intermediate in graft polymerizations, and as crosslink for high molecular weight materials.

  6. Poly(amide-graft-acrylate) interfacial compounds

    NASA Astrophysics Data System (ADS)

    Zamora, Michael Perez

    Graft copolymers with segments of dissimilar chemistries have been shown to be useful in a variety of applications as surfactants, compatibilizers, impact modifiers, and surface modifiers. The most common route to well defined graft copolymers is through the use of macromonomers, polymers containing a reactive functionality and thus capable of further polymerization. However, the majority of the studies thus far have focused on the synthesis of macromonomers capable of reacting with vinyl monomers to form graft copolymers. This study focused on the synthesis of macromonomers capable of participating in condensation polymerizations. A chain transfer functionalization method was utilized. Cysteine was evaluated as a chain transfer agent for the synthesis of amino acid functionalized poly(acrylate) and poly(methacrylate) macromonomers. Low molar mass, functionalized macromonomers were produced. These macromonomers were proven to be capable of reacting with amide precursors to form poly(amide-g-acrylate) graft copolymers. Macromonomers and graft copolymers were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, elemental analysis (EA), inductively coupled plasma (ICP), and differential scanning calorimetry (DSC). The second part of this research involved poly(dimethacrylate) dental restorative materials. Volumetric shrinkage during the cure of these resins results in a poor interface between the resin and the remaining tooth structure, limiting the lifetime of these materials. Cyclic anhydrides were incorporated into common monomer compositions used in dental applications. Volume expansion from the ring opening hydrolysis of these anhydrides was shown to be feasible. The modified dental resins were characterized by swelling, extraction and ultraviolet spectroscopy (UV), and density measurements. Linear poLymers designed to model the crosslinked dental resins were

  7. Grafting of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole onto polymers with aliphatic groups. Synthesis and polymerization of 2 (2-hydroxy-5-isopropenylphenyl) 2H-benzotriazole and a new synthesis of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole

    NASA Technical Reports Server (NTRS)

    Pradellok, W.; Nir, Z.; Vogl, O.

    1981-01-01

    Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C-H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150 C = 160 C with di-tertiarybutylperoxide as the grafting initiator, grafts as high as 20 percent - 30 percent at a grafting efficiency of 50 percent and 80 percent have readily been obtained. The grafting reaction was carried out in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. On a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate were used.

  8. Polymeric materials in Space

    NASA Astrophysics Data System (ADS)

    Skurat, Vladimir

    Paper of short review type. It is the continuation of and addition to previous review papers "V. E. Skurat. Polymers in Space. In: Encyclopedia of aerospace engineering, vol. 4, Wiley and sons, 2010; Ibid., 2012 (on line)". Following topics are considered: (1) Destruction of polymers by solar radiation with various wavelengths in different spectral regions (visible-UV, vacuum UV (VUV), deep UV, soft and hard X-rays) are discussed. In difference with common polymer photochemistry induced by UV radiation, directions of various routs of polymer phototransformations and their relative yields are greatly dependent on wavelength of light (photon energy) during illuminations in VUV, deep UV and X-ray regions. During last twenty years, intensive spacecraft investigations of solar spectrum show great periodic and spontaneous variations of radiation intensities in short-wavelengths regions - up to one - two decimal orders of magnitude for X-rays. As a result, during solar flares the absorbed dose on the polymer surfaces from X-rays can be compared with absorbed dose from VUV radiation. (2) Some new approaches to predictions of reaction efficiencies of fast orbital atomic oxygen in their interaction with polymeric materials are considered. (3) Some aspects of photocatalitic destruction of polymers in vacuum conditions by full-spectrum solar radiation are discussed. This process can take place in enamels containing semiconducting particles (TiO2, ZnO) as pigments. (4) Contamination of spacecraft surfaces from intrinsic outer atmosphere play important role not only from the point of view of deterioration of optical and thermophysical properties. Layers of SiO2 contaminations with nanometer thicknesses can greatly diminish mass losses from perfluorinated polymers under VUV irradiation.

  9. Graft copolymers with immobilized peroxidase for organic synthesis

    NASA Astrophysics Data System (ADS)

    De Queiroz, Alvaro Antonio Alencar; Vargas, Reinaldo Romero; Higa, Olga Zazuco; Barrak, Élcio Rogério; Bechara, Etelvino J. H.; Wlasdislaw, Blanka; Marzorati, Liliana

    1999-07-01

    The graft copolymer poly(propylene)-graft-poly(acrylic acid) (PP-G-AA) was prepared by radiation-induced graft copolymerization of acrylic acid onto polypropylene spheres and characterized by thermal analysis and scanning electron microscopy (SEM). Maximum percentage of grafting (70%) was obtained at a total dose of 12 kGy using 30% (w/w) of acrylic acid. The Michaelis constant, KM, and the maximum reaction velocity, VMax, were determined for the free horseradish peroxidase and for the immobilized horseradish peroxidase. The enzyme affinity for the substrate ( KM/ Vmax) remains quite good after immobilization. The sulfoxidation reaction of a ketosulfide was investigated with the immobilized peroxidase.

  10. Polymerization of perfluorobutadiene

    NASA Technical Reports Server (NTRS)

    Newman, J.; Toy, M. S.

    1970-01-01

    Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

  11. Flocculation properties of polyacrylamide grafted carboxymethyl guar gum (CMG-g-PAM) synthesised by conventional and microwave assisted method.

    PubMed

    Pal, Sagar; Ghorai, S; Dash, M K; Ghosh, S; Udayabhanu, G

    2011-09-15

    A novel polymeric flocculant based on polyacrylamide grafted carboxymethyl guar gum (CMG-g-PAM) has been synthesised by grafting polyacrylamide chains onto CMG backbone using conventional redox grafting and microwave assisted grafting methods. Under optimum grafting conditions, 82% and 96% grafting efficiencies have been observed in case of conventional and microwave assisted methods respectively. The optimum sample has been characterized using viscometry, spectroscopic analysis, elemental analysis, molecular weight and radius of gyration determination. The flocculation characteristics of grafted and ungrafted polysaccharides have been evaluated in kaolin suspension, municipal sewage wastewater and decolourization efficiency of a dye solution (methylene blue). It is evident from results that CMG-g-PAM synthesised by microwave assisted grafting method is showing best flocculation characteristics. PMID:21802849

  12. Polymerization Reactor Engineering.

    ERIC Educational Resources Information Center

    Skaates, J. Michael

    1987-01-01

    Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

  13. Effects of T cell depletion in radiation bone marrow chimeras. III. Characterization of allogeneic bone marrow cell populations that increase allogeneic chimerism independently of graft-vs-host disease in mixed marrow recipients

    SciTech Connect

    Sykes, M.; Chester, C.H.; Sundt, T.M.; Romick, M.L.; Hoyles, K.A.; Sachs, D.H. )

    1989-12-01

    The opposing problems of graft-vs-host disease vs failure of alloengraftment severely limit the success of allogeneic bone marrow transplantation as a therapeutic modality. We have recently used a murine bone marrow transplantation model involving reconstitution of lethally irradiated mice with mixtures of allogeneic and syngeneic marrow to demonstrate that an allogeneic bone marrow subpopulation, removed by T cell depletion with rabbit anti-mouse brain serum and complement (RAMB/C), is capable of increasing levels of allogeneic chimerism. This effect was observed in an F1 into parent genetic combination lacking the potential for graft-vs-host disease, and radiation protection studies suggested that it was not due to depletion of stem cells by RAMB/C. We have now attempted to characterize the cell population responsible for increasing allogeneic chimerism in this model. The results indicate that neither mature T cells nor NK cells are responsible for this activity. However, an assay involving mixed marrow reconstitution in an Ly-5 congenic strain combination was found to be more sensitive to small degrees of stem cell depletion than radiation protection assays using three-fold titrations of bone marrow cells. Using this assay, we were able to detect some degree of stem cell depletion by treatment with RAMB/C, but not with anti-T cell mAb. Nevertheless, if the effects of alloresistance observed in this model are considered, the degree of stem cell depletion detected by such mixing studies in insufficient to account for the effects of RAMB/C depletion on levels of allogeneic chimerism, suggesting that another cell population with this property remains to be identified.

  14. Light-responsive polymer surfaces via postpolymerization modification of grafted polymer-brush structures.

    PubMed

    Dübner, Matthias; Spencer, Nicholas D; Padeste, Celestino

    2014-12-16

    Light-induced, spatially well-defined, reversible switching of surface properties enables the creation of remote-controlled smart surfaces. We have taken advantage of the unique high-resolution structuring capabilities of extreme ultraviolet (EUV) interference lithography to produce nanostructured photoresponsive polymer brushes. Patterns of poly(glycidyl methacrylate) (PGMA) and poly(methacrylic acid) (PMAA) were grafted from two different 100 μm thick fluoropolymer substrates by means of a radiation-initiated, grafting-from approach based on free-radical polymerization (FRP). Photochromic properties were introduced via novel one- or two-step postpolymerization modifications with spiropyran (SP) derivatives, which allowed us to control the number of photochromic groups on the polymer brushes. Depending on the degree of functionalization and the local chemical environment, the SP moieties can open upon UV-light exposure to form zwitterionic, deeply colored, and fluorescent merocyanines (MCs) and reclose to the colorless SP configuration via thermal or visible light-induced relaxation. Switching kinetics were studied by means of time-resolved fluorescence microscopy and compared with kinetic measurements of the SP moiety in solution. The results indicated the importance, for the intensity of the switching, of the local chemical environment provided by both the polymer brush and added solvents, and showed the predominant influence on the ring-closing kinetics of polar solvents, which stabilize the MC form. To allow further characterization of the polymer-brush arrangements on a macroscopic scale, similar, but unstructured brush systems were grafted from fluoropolymers after large-area activation using EUV radiation or argon plasma. All steps of the postpolymerization modification were characterized in detail using attenuated total reflection infrared (ATR-IR) spectroscopy. Furthermore, a light-induced reversible static-contact-angle switch with a range of up to 15

  15. Preparation and characterization of grafted imprinted monolith for capillary electrochromatography.

    PubMed

    Wei, Ze-Hui; Mu, Li-Na; Pang, Qian-Qian; Huang, Yan-Ping; Liu, Zhao-Sheng

    2012-10-01

    In this paper, a molecularly imprinted polymer (MIP) coating grafted to a trimethylolpropane trimethacrylate (TRIM) core material for CEC was reported. The core monolith was prepared with a solution of 20% (w/w) TRIM in a mixture of porogen and a polymerization precursor, which can generate a stable electroosmotic flow due to the formation of ionizable groups after postpolymerization hydrolization. Graft polymerization took place on the resultant TRIM monolith with a mixture of template, methacrylic acid, and ethylene glycol dimethacrylate. Strong recognition ability (selectivity factor was 5.83) for S-amlodipine and resolution of enatiomers separation (up to 7.99) were obtained on the resulting grafted imprinted monolith in CEC mode. The influence of CEC conditions on chiral separation, including the composition of mobile phase, pH value, and the operating voltages was studied. These results suggest that the method of grafted polymerization reported here allows a rapid development of MIP monolith once core materials with desired properties are available, and is a good alternative to prepare CEC-based monolithic MIPs. PMID:22996033

  16. Thin Film Deformation Behavior of Polystyrene Grafted Nanoparticle Assemblies

    NASA Astrophysics Data System (ADS)

    Jiao, Yang; Hsiao, Ming-Siao; Drummy, Lawrence; Vaia, Richard

    Assemblies of polymer-grafted ``hairy'' nanoparticles (HNPs) are of current interest for a wide array of mechanical, photonic and electrical applications. In contrast to nanoparticles dispersed in a free polymer matrix, the grafted polymer determines particle spacing and circumvents nanoparticle agglomeration. The extent to which these grafted polymers are entangled determines the robustness and strength of the HNP assembly. Here in, we investigate the correlations between grafted polymer conformation, entanglements and deformation mechanisms of thin film assemblies of polystyrene-grafted HNPs by controlling the HNP architecture (grafting density and molecular weight). HNPs with varied corona structures are synthesized with surface-initiated controlled/living radical polymerization. Thin films with controlled thickness are prepared by flow coating. Plastic deformation of thin films are examined using static (bright field, HAADF-STEM, tomography) and AFM techniques. Results show a decrease of void density in craze as grafted polymer length increases for semi-dilute polymer brushes. These correlations between HNP architecture and assembly deformation and failure modes refine the HNP design space for the synthesis and fabrication of assemblies with excellent mechanical properties.

  17. Heterogeneous polymerizations in supercritical carbon dioxide continuous phases

    SciTech Connect

    DeSimone, J.M.; Maury, E.E.; Combes, J.R.; Menceloglu, Y.Z.

    1993-12-31

    Heterogeneous emulsion polymerizations are important industrial methods for the synthesis of various polymeric materials. These processes generally use water as the dispersing medium. The authors propose to utilize carbon dioxide as the dispersing medium which would make the polymer recovery easier and would circumvent the contamination of water. In CO{sub 2} - based emulsion process one can have either a hydrophilic dispersed phase (hydrophilic monomer) or a hydrophobic dispersed phase (hydrophobic monomer). The surfactant has to be designed to partition itself at the CO{sub 2} - monomer/polymer interface and the initiator has to be soluble in the dispersing medium. The design of the initiator and graft copolymer surfactants will be presented. One example of a graft copolymer is a copolymer of poly(ethylene oxide) macromonomer synthesized by living anionic polymerization and a fluoroacrylate monomer resulting in a graft copolymer having hydrophilic grafts and a {open_quotes}CO{sub 2}-philic{close_quotes} backbone (due to the fluorine chains). The phase behavior of these surfactants will be discussed at the meeting.

  18. Evaluation of a cesium adsorbent grafted with ammonium 12-molybdophosphate

    NASA Astrophysics Data System (ADS)

    Shibata, Takuya; Seko, Noriaki; Amada, Haruyo; Kasai, Noboru; Saiki, Seiichi; Hoshina, Hiroyuki; Ueki, Yuji

    2016-02-01

    A fibrous cesium (Cs) adsorbent was developed using radiation-induced graft polymerization with a cross-linked structure containing a highly stable adsorption ligand. The ligand, ammonium 12-molybdophosphate (AMP), was successfully introduced onto the fibrous polyethylene trunk material. The resulting Cs adsorbent contained 36% nonwoven fabric polyethylene (NFPE), 1% AMP, 2% triallyl isocyanurate (TAIC) and 61% glycidyl methacrylate (GMA). The adsorbent's Cs adsorption capacity was evaluated using batch and column tests. It was determined that the adsorbent could be used in a wide pH range. The amount of desorbed molybdenum, which can be used as an estimate for AMP stability on the Cs adsorbent, was minimized at the standard drinking water pH range of 5.8-8.6. Based from the inspection on the adherence of these results to the requirements set forth by the Food Sanitation Act by a third party organization, it can be concluded that the developed Cs adsorbent can be safely utilized for drinking water.

  19. Hydroxyalkylation and polyether polyol grafting of graphene tailored for graphene/polyurethane nanocomposites.

    PubMed

    Appel, Anna-Katharina; Thomann, Ralf; Mülhaupt, Rolf

    2013-08-01

    Graphene functionalization by hydroxyalkylation and grafting with polyether polyols enables polyurethane (PU) nanocomposites formation by in situ polymerization with isocyanates combined with effective covalent interfacial coupling. Functionalized graphene (FG) hydroxylation is achieved either by alkylation, transesterification, or grafting of thermally reduced graphite oxide. In the presence of K2 CO3 as catalyst the reaction of FG-OH with ethylene carbonate at 180 °C affords hydroxyethylated FG, whereas transesterification with castor oil produces riconoleiate-modified FG polyols. In the "grafting-from" process, FG-alkoholate macro initiators initiate the graft polymerization of propylene oxide to produce hybrid FG polyols containing 38 and 59 wt% oligopropylene oxide. In the "grafting-to" process 3-ethyl-3-hydroxymethyl-oxetane is cationically polymerized onto FG-OH, producing novel hyperbranched FG-based polyether polyols. Whereas hydroxylation and grafting of FG greatly improve FG dispersion in organic solvents, polyols and even PU, as confirmed by transmission electron microscopy, matrix reinforcement of FG/PU is impaired by increasing alkyl chain length and polyol graft copolymer content. PMID:23836705

  20. Monolithic molecularly imprinted polymeric capillary columns for isolation of aflatoxins.

    PubMed

    Szumski, Michał; Grzywiński, Damian; Prus, Wojciech; Buszewski, Bogusław

    2014-10-17

    Monolithic molecularly imprinted polymers extraction columns have been prepared in fused-silica capillaries by UV or thermal polymerization in a two-step process. First, a poly-(trimethylolpropane trimethacrylate) (polyTRIM) core monolith was synthesized either by UV or thermal polymerization. Then it was grafted with the mixture of methacrylic acid (MAA) as a functional monomer, ethylene dimethacrylate (EDMA) as a cross-linking agent, 5,7-dimethoxycoumarin (DMC) as an aflatoxin-mimicking template, toluene as a porogen solvent and 2,2-azobis-(2-methylpropionitrile) (AIBN) as an initiator of the polymerization reaction. Different thermal condition of the photografting and different concentrations of the grafting mixture were tested during polymerization. The extraction capillary columns were evaluated in the terms of their hydrodynamic and chromatographic properties. Retention coefficients for aflatoxin B1 and DMC were used for assessment of the selectivity and imprinting factor. The obtained results indicate that the temperature of photografting and concentration of the grafting mixture are key parameters that determine the quality of the prepared MIPs. From the MIP columns characterized by the highest permeability the column of the highest imprinting factor was applied for isolation of aflatoxins B1, B2, G1 and G2 from the model aqueous sample followed by on-line chromatographic separation. The process was performed using a micro-MISPE-microLC-LIF system of a novel design, which allowed for detection of the eluates from the sample preparation part as well as from the chromatographic separation. PMID:25218633

  1. Preparation and evaluation of inhalable itraconazole chitosan based polymeric micelles

    PubMed Central

    2012-01-01

    Background This study evaluated the potential of chitosan based polymeric micelles as a nanocarrier system for pulmonary delivery of itraconazole (ITRA). Methods Hydrophobically modified chitosan were synthesized by conjugation of stearic acid to the hydrophilic depolymerized chitosan. FTIR and 1HNMR were used to prove the chemical structure and physical properties of the depolymerized and the stearic acid grafted chitosan. ITRA was entrapped into the micelles and physicochemical properties of the micelles were investigated. Fluorescence spectroscopy, dynamic laser light scattering and transmission electron microscopy were used to characterize the physicochemical properties of the prepared micelles. The in vitro pulmonary profile of polymeric micelles was studied by an air-jet nebulizer connected to a twin stage impinger. Results The polymeric micelles prepared in this study could entrap up to 43.2±2.27 μg of ITRA per milliliter. All micelles showed mean diameter between 120–200 nm. The critical micelle concentration of the stearic acid grafted chitosan was found to be 1.58×10-2 mg/ml. The nebulization efficiency was up to 89% and the fine particle fraction (FPF) varied from 38% to 47%. The micelles had enough stability to remain encapsulation of the drug during nebulization process. Conclusions In vitro data showed that stearic acid grafted chitosan based polymeric micelles has a potential to be used as nanocarriers for delivery of itraconazole through inhalation. PMID:23351398

  2. Hybrid rigid/soft and biologic/synthetic materials: polymers grafted onto cellulose microcrystals.

    PubMed

    Harrisson, Simon; Drisko, Glenna L; Malmström, Eva; Hult, Anders; Wooley, Karen L

    2011-04-11

    Rigid nanoscale polymer rods were prepared by grafting preformed amine-terminated poly(styrene) and poly(tert-butyl acrylate) onto oxidized cellulose microcrystals. Low polydispersity polymers, grown using atom transfer radical polymerization, were characterized and purified prior to cellulose attachment. Oxidation of the cellulose microcrystal led to the formation of carboxylic acids on the surface of the microcrystals. Covalent attachment of the polymers onto the cellulose microcrystals was achieved via a carbodiimide-mediated amidation reaction. The length and diameter of the polymer-cellulose composites increased upon surface modification. Typically, polymer-cellulose composites are synthesized by a grafting-from method because it can be difficult to obtain sufficient graft density using a grafting-to preparation. However, the composites reported here comprised 60-64% grafted polymer by mass. This degree of grafting-to allowed the composite to form stable suspensions in organic solvents. PMID:21381766

  3. Surface Modification of PET Fabric by Graft Copolymerization with Acrylic Acid and Its Antibacterial Properties

    PubMed Central

    Abdolahifard, M.; Bahrami, S. Hajir; Malek, R. M. A.

    2011-01-01

    Graft copolymerization of acrylic acid (AA) onto Poly(ethylene terephthalate) (PET) fabrics with the aid of benzoyl peroxide was carried out. The effect of polymerization parameters on the graft yield was studied. Percent grafting was enhanced significantly by increasing benzoyl peroxide (BP) concentrations up to 3.84 g/lit and then decreased upon further increase in initiator concentration. Preswelling of PET leads to changes in its sorption-diffusion properties and favors an increase in the degree of grafting. The antibiotics treated grafted fabrics showed antibacterial properties towards gram-positive and gram-negative microorganisms. FTIR and SEM were used to characterize AA-grafted polyester fabrics. PMID:24052819

  4. PVDF multifilament yarns grafted with polystyrene induced by γ-irradition: Influence of the grafting parameters on the mechanical properties

    NASA Astrophysics Data System (ADS)

    Marmey, P.; Porté, M. C.; Baquey, Ch.

    2003-08-01

    The development of alternative prosthetic materials for cardiovascular applications has found growing interest due to the failure to date to be able to implement functional patent small diameter vascular grafts (∅<5 mm). For instance, the successful implantation of small diameter polyester (PET) and expanded polytetrafluoroethylene (PTFEe) vascular grafts has not been achieved in humans. Our stategy is to work with a new multifilament yarns biomaterial, produced from polyvinylidene fluoride (PVDF), which shows suitable mechanical properties, such as a lower tensile modulus than PET and PTFEe. The required biological properties sought for (i.e. low thrombogenicity) could be achieved by "heparin-like" surface modification treatments in order to modify the thrombogenicity levels of the polymeric materials [Ann. Biomed. Eng. 7 (1979) 429]. A four step method is necessary to achieve this "heparin-like" surface transformation [J. Biomed. Mater. Res. 52 (2000) 119]. The first step consists in grafting polystyrene onto the PVDF surface by γ irradiation. The purpose of this study was to evaluate the influence of grafting parameters on the mechanical properties: (i) γ-ray irradiation time and (ii) grafting time of styrene monomers, which polymerize and form polystyrene bound to the PVDF surface.

  5. A Versatile Star PEG Grafting Method for the Generation of Nonfouling and Nonthrombogenic Surfaces

    PubMed Central

    Thalla, Pradeep Kumar; Contreras-García, Angel; Fadlallah, Hicham; Barrette, Jérémie; De Crescenzo, Gregory; Merhi, Yahye; Lerouge, Sophie

    2013-01-01

    Polyethylene glycol (PEG) grafting has a great potential to create nonfouling and nonthrombogenic surfaces, but present techniques lack versatility and stability. The present work aimed to develop a versatile PEG grafting method applicable to most biomaterial surfaces, by taking advantage of novel primary amine-rich plasma-polymerized coatings. Star-shaped PEG covalent binding was studied using static contact angle, X-ray photoelectron spectroscopy (XPS), and quartz crystal microbalance with dissipation monitoring (QCM-D). Fluorescence and QCM-D both confirmed strong reduction of protein adsorption when compared to plasma-polymerized coatings and pristine poly(ethyleneterephthalate) (PET). Moreover, almost no platelet adhesion was observed after 15 min perfusion in whole blood. Altogether, our results suggest that primary amine-rich plasma-polymerized coatings offer a promising stable and versatile method for PEG grafting in order to create nonfouling and nonthrombogenic surfaces and micropatterns. PMID:23509823

  6. Design of modified plastic surfaces for antimicrobial applications: Impact of ionizing radiation on the physical and mechanical properties of polypropylene

    NASA Astrophysics Data System (ADS)

    Riquet, Anne-Marie; Delattre, Jennifer; Vitrac, Olivier; Guinault, Alain

    2013-10-01

    Surface modification of polypropylene (PP) sheets was carried out by radiation induced graft polymerization of hydrophilic functional molecules such as N,N-dimethylacrylamide (DMA) and [2-methacryloyloxy)ethyl] trimethylammonium chloride, which is a quaternary ammonium salt (QAS). Polypropylene sheets were activated prior to the grafting reaction by using electron beam radiation. The changes in morphology, crystallinity and tensile parameters like deformation and stress at yield and deformation at break of PP after irradiation were investigated. The results showed that a minor crystalline reorganization takes place during the irradiation of PP at 100 kGy. The grafting has been observed to be strongly dependent on the monomer dilution in the reaction medium. After grafting of QAS (40%) and DMA (20%) it was possible to develop highly hydrophilic surfaces (water contact angle comprised between 30 and 41°). The surfaces of virgin, irradiated and grafted PP were studied using polarized optical microscopy (POM) and scanning electron microscopy (SEM). Spherical particles (i.e. polystyrene or silica beads) adhering to the modified samples were studied according to the surface parameters. Adhesion tests confirmed the strong influence of substrate type (mainly hydrophilicity and roughness) and to a lesser extent underlined the role of electrostatic interactions for the design of plastic surfaces for antimicrobial applications.

  7. A device for a noninvasive evaluation of coronary bypass grafts.

    PubMed

    McInerney, J J; Lamser, D G; Herr, M D

    1994-01-01

    A new device is presented for evaluating the patency of coronary bypass grafts. Bypass grafts are located within the chest cavity using a Compton backscatter imaging (CBI) technique that creates frontal plane tomographic images. The tomographic image pixels are mapped into computer memory and displayed. A display pointer is used to mark the position of the bypass graft. The computer uses that information to subsequently position a radiation detector, such that it "looks" at the location of the bypass graft within the closed chest. The patency of the graft is then evaluated by monitoring an X-ray induced iodine fluorescence transient in the graft, subsequent to a peripheral intravenous contrast injection. This imaging and graft evaluation device is relatively inexpensive and its application does not require cutdowns or catheterization. The associated radiation dose is 1/10 to 1/50 of that associated with alternative X-ray graft patency evaluation techniques. Preliminary testing has been performed on mechanical and animal models. PMID:18218544

  8. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  9. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  10. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  11. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  12. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  13. Do Stem Cells Have an Effect When We Fat Graft?

    PubMed

    Rinker, Brian D; Vyas, Krishna S

    2016-06-01

    Fat grafting has become a widely accepted modality of soft tissue restoration and has found applications in many areas of aesthetic and reconstructive plastic surgery. Numerous claims have been made regarding the regenerative effects of fat grafting on the recipient bed. The purpose of this paper is to survey the available literature to answer the question of whether fat grafting has a positive effect on the surrounding tissues. It has been convincingly demonstrated that fat grafts contain viable adipose-derived stem cells (ASCs). The fate of these cells is determined by the microenvironment of the recipient bed, but animal studies have shown that a large fraction of ASCs survive engraftment. Numerous clinical studies have demonstrated the positive effects of fat grafting on recipient tissues. Improvement in validated scar scores as well as scar stiffness measurements have been documented after fat grafting of burn scars. Fat grafting has also been convincingly demonstrated to improve the quality of irradiated tissues, as measured by validated clinical scales and staged histology. It is ultimately unclear whether ASCs are responsible for these effects, but the circumstantial evidence is weighty. Fat grafting is effective for volumizing and improving skin quality in the setting of radiation, burns, and other scars. The observed effects are likely due to ASCs, but the evidence does not support the routine use of ASC-enriched fat grafts. PMID:26545225

  14. Free radical grafting kinetics of acrylamide onto a blend of starch/chitosan/alginate.

    PubMed

    Sorour, Mohamed; El-Sayed, Marwa; El Moneem, Nabil Abd; Talaat, Hala; Shaalan, Hayam; El Marsafy, Sahar

    2013-10-15

    Grafting of monomer onto polymer backbone is one of the effective and accessible methods for the chemical modification of polysaccharides. Grafting of acrylamide (AAm) onto polysaccharides blend (PsB) composed of starch, chitosan and alginate has been carried out using potassium persulfate (KPS) as an initiator. The kinetics of the grafting polymerization also has been studied. The grafting parameters have been evaluated by changing the initial concentrations of AAm from 8 to 16 g, PsB from 6 to 14 g and KPS from 0.2 to 1 g. Evidence of grafting has been obtained from FTIR, XRD and TGA. The kinetics of the grafting polymerization also has been studied. The grafting rate equation of the produced hydrogel (PsB-g-AAm) hydrogel has been expressed by: Rg=k[AAm] [PsB](0.5) [KPS](0.5). The grafting rate is a first order dependence to [AAm] initial concentration and square root to [PsB] and [KPS] initial concentrations in the used concentrations range. PMID:23987368

  15. Ferritin-Polymer Conjugates: Grafting Chemistry and Integration into Nanoscale Assemblies

    SciTech Connect

    Y Hu; D Samanta; S Parelkar; S Hong; Q Wang; T Russell; T Emrick

    2011-12-31

    Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylene oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.

  16. Controlled atom transfer radical polymerization of MMA onto the surface of high-density functionalized graphene oxide

    PubMed Central

    2014-01-01

    We report on the grafting of poly(methyl methacrylate) (PMMA) onto the surface of high-density functionalized graphene oxides (GO) through controlled radical polymerization (CRP). To increase the density of surface grafting, GO was first diazotized (DGO), followed by esterification with 2-bromoisobutyryl bromide, which resulted in an atom transfer radical polymerization (ATRP) initiator-functionalized DGO-Br. The functionalized DGO-Br was characterized by X-ray photoelectron spectroscopy (XPS), Raman, and XRD patterns. PMMA chains were then grafted onto the DGO-Br surface through a ‘grafting from’ technique using ATRP. Gel permeation chromatography (GPC) results revealed that polymerization of methyl methacrylate (MMA) follows CRP. Thermal studies show that the resulting graphene-PMMA nanocomposites have higher thermal stability and glass transition temperatures (Tg) than those of pristine PMMA. PMID:25114639

  17. Controlled atom transfer radical polymerization of MMA onto the surface of high-density functionalized graphene oxide

    NASA Astrophysics Data System (ADS)

    Kumar, Mukesh; Chung, Jin Suk; Hur, Seung Hyun

    2014-07-01

    We report on the grafting of poly(methyl methacrylate) (PMMA) onto the surface of high-density functionalized graphene oxides (GO) through controlled radical polymerization (CRP). To increase the density of surface grafting, GO was first diazotized (DGO), followed by esterification with 2-bromoisobutyryl bromide, which resulted in an atom transfer radical polymerization (ATRP) initiator-functionalized DGO-Br. The functionalized DGO-Br was characterized by X-ray photoelectron spectroscopy (XPS), Raman, and XRD patterns. PMMA chains were then grafted onto the DGO-Br surface through a `grafting from' technique using ATRP. Gel permeation chromatography (GPC) results revealed that polymerization of methyl methacrylate (MMA) follows CRP. Thermal studies show that the resulting graphene-PMMA nanocomposites have higher thermal stability and glass transition temperatures ( T g) than those of pristine PMMA.

  18. Biology of cancellous bone grafts.

    PubMed

    Heiple, K G; Goldberg, V M; Powell, A E; Bos, G D; Zika, J M

    1987-04-01

    Despite 30 years of experimental bone grafting research, the fresh cancellous bone graft remains the most osteogenic and reliable bone grafting material. Recent experimental data suggest that modification of the graft-host interaction by antigen matching or immune manipulation may allow increasingly successful use of allografts. PMID:3550570

  19. Bioactive Polymer Grafting onto Titanium Alloy Surfaces for Improved Osteointegration

    PubMed Central

    Michiardi, Alexandra; Hélary, Gérard; Nguyen, Phuong-Cac Thi; Gamble, Lara J.; Anagnostou, Fani; Castner, David G.; Migonney, Véronique

    2013-01-01

    Bioactive polymers bearing sulfonate (styrene sodium sulfonate, NaSS) and carboxylate (methylacrylic acid, MA) groups were grafted onto Ti6Al4V alloy surfaces by a two-step procedure. The Ti alloy surfaces were first chemically oxidized in a piranha solution and then directly subjected to radical polymerization at 70°C in absence of oxygen. The grafted surfaces were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and the Toluidin blue colorimetric method. Toluidin blue results showed 1 to 5 μg/cm2 of polymer was grafted onto the oxidized Ti surfaces. Grafting resulted in a decrease in the XPS Ti and O signals from the underlying Ti substrate and a corresponding increase in the XPS C and S signals from the polymer layer. The ToF-SIMS intensities of the S− and SO− ions correlated linearly with the XPS atomic percent S concentrations and the ToF-SIMS intensity of the TiO3H2− ion correlated linearly with the XPS atomic percent Ti concentration. Thus, the ToF-SIMS S−, SO− and TiO3H2− intensities can be used to quantify composition and amount of grafted polymer. ToF-SIMS also detected ions that were more characteristic of the polymer molecular structure (C6H4SO3− and C8H7SO3− from NaSS, C4H5O2− from MA), but the intensity of these peaks depended on the polymer thickness and composition. An in vitro cell culture test was carried out with human osteoblast-like cells to assess the influence of the grafted polymers on cell response. Cell adhesion after 30 min of incubation showed significant differences between the grafted and un-grafted surfaces. The NaSS grafted surfaces showed the highest degree of cell adhesion while the MA-NaSS grafted surfaces showed the lowest degree of cell adhesion. After 4 weeks in vivo in rabbit femoral bones bone was observed to be in direct contact with all implants. The percent of mineralized tissue around the implants was similar for NaSS grafted and non-grafted

  20. Activation of polymeric materials towards enzymatic postgrafting and cross-linking.

    PubMed

    Fatarella, E; Ciabatti, I; Cortez, J

    2012-10-10

    A methodology to activate inert polymeric materials to enzymatic functionalisation is described herein. Plasma irradiation can be used to graft compounds containing a moiety that is reactive towards an enzyme of interest. Subsequently, such enzyme can be used to either postgraft functional compounds or cross-link the polymeric materials. Argon plasma was utilised to graft 2-aminoethyl methacrylate onto cotton and wool fibres, introducing surface alkylamine groups to impart reactivity towards transglutaminase and tyrosinase. The efficiency of plasma grafting was verified by ATR-FTIR. Enzyme postgrafting of fluorescent peptides coupled with confocal microscopy was used to demonstrate transglutaminase activity towards cotton, a material typically inert to this enzyme. The grafting of alkylamines onto wool resulted in additional cross-linking by both enzymes, leading to significantly increased yarn breaking load and elongation at break. This technology permits the activation of inert materials towards enzymatic postgrafting, with applications in fields as diverse as textiles and biomaterials. PMID:22975121

  1. Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

    NASA Astrophysics Data System (ADS)

    He, Chunli; Wang, Miao; Cai, Xianmei; Huang, Xiaobo; Li, Li; Zhu, Haomiao; Shen, Jian; Yuan, Jiang

    2011-11-01

    To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm2 for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.

  2. Surface modification of polydimethylsiloxane with photo-grafted poly(ethylene glycol) for micropatterned protein adsorption and cell adhesion.

    PubMed

    Sugiura, Shinji; Edahiro, Jun-ichi; Sumaru, Kimio; Kanamori, Toshiyuki

    2008-06-01

    In this study, we applied photo-induced graft polymerization to micropatterned surface modification of polydimethylsiloxane (PDMS) with poly(ethylene glycol). Two types of monomers, polyethylene glycol monoacrylate (PEGMA) and polyethylene glycol diacrylate (PEGDA), were tested for surface modification of PDMS. Changes in the surface hydrophilicity and surface element composition were characterized by contact angle measurement and electron spectroscopy for chemical analysis. The PEGMA-grafted PDMS surfaces gradually lost their hydrophilicity within two weeks. In contrast, the PEGDA-grafted PDMS surface maintained stable hydrophilic characteristics for more than two months. Micropatterned protein adsorption and micropatterned cell adhesion were successfully demonstrated using PEGDA-micropatterned PDMS surfaces, which were prepared by photo-induced graft polymerization using photomasks. The PEGDA-grafted PDMS exhibited useful characteristics for microfluidic devices (e.g. hydrophilicity, low protein adsorption, and low cell attachment). The technique presented in this study will be useful for surface modification of various research tools and devices. PMID:18242961

  3. Tissue engineered small-diameter vascular grafts.

    PubMed

    Schmedlen, Rachael H; Elbjeirami, Wafa M; Gobin, Andrea S; West, Jennifer L

    2003-10-01

    Arterial occlusive disease remains the leading cause of death in western countries and often requires vascular reconstructive surgery. The limited supply of suitable small-diameter vascular grafts has led to the development of tissue engineered blood vessel substitutes. Many different approaches have been examined, including natural scaffolds containing one or more ECM proteins and degradable polymeric scaffolds. For optimal graft development, many efforts have modified the culture environment to enhance ECM synthesis and organization using bioreactors under physiologic conditions and biochemical supplements. In the past couple of decades, a great deal of progress on TEVGs has been made. Many challenges remain and are being addressed, particularly with regard to the prevention of thrombosis and the improvement of graft mechanical properties. To develop a patent TEVG that grossly resembles native tissue, required culture times in most studies exceed 8 weeks. Even with further advances in the field, TEVGs will likely not be used in emergency situations because of the time necessary to allow for cell expansion, ECM production and organization, and attainment of desired mechanical strength. Furthermore, TEVGs will probably require the use of autologous tissue to prevent an immunogenic response, unless advances in immune acceptance render allogenic and xenogenic tissue use feasible. TEVGs have not yet been subjected to clinical trials, which will determine the efficacy of such grafts in the long term. Finally, off-the-shelf availability and cost will become the biggest hurdles in the development of a feasible TEVG product. Although many obstacles exist in the effort to develop a small-diameter TEVG, the potential benefits of such an achievement are exciting. In the near future, a nonthrombogenic TEVG with sufficient mechanical strength may be developed for clinical trials. Such a graft will have the minimum characteristics of biological tissue necessary to remain patent

  4. Superhydrophocity via gas-phase monomers grafting onto carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zha, Jinlong; Batisse, Nicolas; Claves, Daniel; Dubois, Marc; Frezet, Lawrence; Kharitonov, Alexander P.; Alekseiko, Leonid N.

    2016-05-01

    Superhydrophobic films were prepared using dispersions of fluorinated multi-walled carbon nanotubes (MWCNTs) or nanofibers (CNFs) in toluene. The grafting of polystyrene allowed stable dispersions to be obtained. The grafting of polystyrene (PS), polyacrylic acid (PAA) and polyaniline (PANI) onto nanofibers and MWCNTs was first evidenced by solid state NMR and Infrared Spectroscopy. The graft polymerization of styrene, acrylic acid and aniline monomers was initiated by radicals (dangling bonds) formed due to the initial fluorination. The process appeared as highly versatile and efficient for different polymers. The consumption of those radicals in the course of grafting was evidenced by EPR, through decrease of the spin density. The hydrophobic/hydrophilic character was tuned according to the grafted polymer nature, i.e. hydrophobic with PS or hydrophilic with PAA. Finally, in order to reach superhydrophobicity, films were prepared from CNFs or MWCNTs, irrespective of their average diameter, that allowed adequate structuring of the surface. The presence of fluorine atoms on their surface also favors superhydrophobicity. Water contact angles of 155 ± 2° and 159 ± 2° were measured for the films casted from fluorinated CNFs or MWCNTs with grafted polystyrene, respectively.

  5. High compliance vascular grafts based on semi-interpenetrating networks

    PubMed Central

    Dempsey, David K.; Nezarati, Roya M.; Mackey, Calvin E.

    2014-01-01

    Current synthetic vascular grafts have poor patency rates in small diameter applications (<6 mm) due to intimal hyperplasia arising from a compliance mismatch between the graft and native vasculature. Enormous efforts have focused on improving biomechanical properties; however, polymeric grafts are often constrained by an inverse relationship between burst pressure and compliance. We have developed a new, semi-interpenetrating network (semi-IPN) approach to improve compliance without sacrificing burst pressure. The effects of heat treatment on graft morphology, fiber architecture, and resultant biomechanical properties are presented. In addition, biomechanical properties after equilibration at physiological temperature were investigated in relation to polyurethane microstructure to better predict in vivo performance. Compliance values as high as 9.2 ± 2.7 %/mmHg x 10−4 were observed for the semi-IPN graft while also maintaining high burst pressure, 1780 ± 230 mm Hg. The high compliance of these heat-treated poly(carbonate urethane) (PCU) and semi-IPN grafts is expected to improve long-term patency rates beyond even saphenous vein autografts by preventing intimal hyperplasia. The fundamental structure-property relationships gained from this work may also be utilized to advance biomedical device designs based on thermoplastic polyurethanes. PMID:25601822

  6. Insitu grafting silica nanoparticles reinforced nanocomposite hydrogels

    NASA Astrophysics Data System (ADS)

    Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang; Xu, Feng; Sun, Run-Cang

    2013-10-01

    Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties.Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties. Electronic supplementary information (ESI) available: FTIR spectra of SNP after silane treatment, dynamic oscillatory shear measurements as a function of frequency, constrained polymer chain analysis by a change in the peak height in loss factor spectra, molecular weight of grafted chains at different stages of gelation, prediction of the SNP reinforcing mechanism in the

  7. Proximal Tibial Bone Graft

    MedlinePlus

    ... Complications Potential problems after a PTBG include infection, fracture of the proximal tibia and pain related to the procedure. Frequently Asked Questions If proximal tibial bone graft is taken from my knee, will this prevent me from being able to ...

  8. Epidermal skin grafting.

    PubMed

    Herskovitz, Ingrid; Hughes, Olivia B; Macquhae, Flor; Rakosi, Adele; Kirsner, Robert

    2016-09-01

    Autologous skin grafts, such as full- and split-thickness, have long been part of the reconstructive ladder as an option to close skin defects. Although they are effective in providing coverage, they require the need for a trained surgeon, use of anaesthesia and operating room and creation of a wound at the donor site. These drawbacks can be overcome with the use of epidermal skin grafts (ESGs), which can be harvested without the use of anaesthesia in an office setting and with minimal to no scarring at the donor site. ESGs consist only of the epidermal layer and have emerged as an appealing alternative to other autologous grafts for the treatment of acute and chronic wounds. In this article, we provide an overview of epidermal grafting and its role in wound management. PMID:27547964

  9. Fabrication of Thiol-Ene "Clickable" Copolymer-Brush Nanostructures on Polymeric Substrates via Extreme Ultraviolet Interference Lithography.

    PubMed

    Dübner, Matthias; Gevrek, Tugce N; Sanyal, Amitav; Spencer, Nicholas D; Padeste, Celestino

    2015-06-01

    We demonstrate a new approach to grafting thiol-reactive nanopatterned copolymer-brush structures on polymeric substrates by means of extreme ultraviolet (EUV) interference lithography. The copolymer brushes were designed to contain maleimide functional groups as thiol-reactive centers. Fluoropolymer films were exposed to EUV radiation at the X-ray interference lithography beamline (XIL-II) at the Swiss Light Source, in order to create radical patterns on their surfaces. The radicals served as initiators for the copolymerization of thiol-ene "clickable" brushes, composed of a furan-protected maleimide monomer (FuMaMA) and different methacrylates, namely, methyl methacrylate (MMA), ethylene glycol methyl ether methacrylate (EGMA), or poly(ethylene glycol) methyl ether methacrylate (PEGMA). Copolymerization with ethylene-glycol-containing monomers provides antibiofouling properties to these surfaces. The number of reactive centers on the grafted brush structures can be tailored by varying the monomer ratios in the feed. Grafted copolymers were characterized by using attenuated total reflection infrared (ATR-IR) spectroscopy. The reactive maleimide methacrylate (MaMA) units were utilized to conjugate thiol-containing moieties using the nucleophilic Michael-addition reaction, which proceeds at room temperature without the need for any metal-based catalyst. Using this approach, a variety of functionalities was introduced to yield polyelectrolytes, as well as fluorescent and light-responsive polymer-brush structures. Functionalization of the brush structures was demonstrated via ATR-IR and UV-vis spectroscopy and fluorescence microscopy, and was also indicated by a color switch. Furthermore, grafted surfaces were generated via plasma activation, showing a strongly increased wettability for polyelectrolytes and a reversible switch in static water contact angle (CA) of up to 18° for P(EGMA-co-MaMA-SP) brushes, upon exposure to alternating visible and UV-light irradiation

  10. Sizing of crimped Dacron grafts.

    PubMed

    Reid, J D; Sladen, J G

    1992-05-01

    The aim of this study was to correlate the stated size of Dacron grafts (Microvel) with their actual internal diameter and to compare this with measurements by ultrasound in the early postoperative period. Grafts of stated diameters of 7, 8, 9, and 10 mm were studied. Grafts were measured by graded probes and by measuring the width of the longitudinally opened graft and calculating the diameter. Each graft accepted a probe 1 mm larger than its stated size very easily and 2 mm greater when stretched. By open measurement, the grafts were 1.3 to 1.8 mm greater than their stated diameter without stretching. Twenty grafts were studied by duplex ultrasound for diameter and peak systolic velocity within 3 months of implantation. The grafts were 12% larger than their stated graft size. Some of the larger grafts showed low velocity and wall thrombus. We conclude that Microvel grafts are larger than their stated diameter. The same size discrepancy was seen in in vitro measurements of Vascutek (Dacron) grafts but not in polytetrafluoroethylene (Gortex) grafts. Since flow velocity is related to the diameter of the graft, this information should be useful when choosing the diameter of a prosthetic vascular graft. PMID:1533494

  11. [Zaidemberg's vascularized radial graft].

    PubMed

    Saint-Cast, Y

    2010-12-01

    In 1991, Carlos Zaidemberg described a new technique to repair scaphoid non-unions with a vascularized bone graft harvested from the radial styloid process. An anatomic study based on 30 dissections after colorized latex injection established the constancy of the radial styloid process's artery, while showing that its origin, course and length were subject to variations. In a retrospective series of 38 cases over a period of 10 years, the vascularized bone graft was indicated for: (1) scaphoid non-union with the presence of avascular changes of the proximal fragment (23 cases); (2) failed prior reconstruction with bone graft and internal fixation (nine cases); (3) degenerative styloid-scaphoid arthritis (three cases); (4) fracture on Preiser dystrophy (three cases). The five steps of the simplified operative technique without dissection of the vascular pedicle include: (1) longitudinal dorso-radial approach, identification of the periosteal portion of the radial styloid process artery; (2) incision of the first and second compartments, longitudinal arthrotomy under the second compartment; (3) styloidectomy and transversal resection of the scaphoid non-union and sclerotic bone; (4) elevation of the vascularized bone graft; (5) transversal and radial insertion of the vascularized bone graft, osteosynthesis by two or three K-wire touching the scaphoid's radial edge. Scaphoid union was obtained in 33 cases out of 38. The only postoperative complications were two transient radial paresthesia. The standardized surgical procedure using vascularized bone graft harvested from the radial styloid process provides an efficient scaphoid reconstruction. PMID:21087882

  12. Phase Behavior and Significantly Enhanced Toughness in Polylactide Graft Copolymers

    NASA Astrophysics Data System (ADS)

    Robertson, Megan; Theryo, Grayce; Jing, Feng; Hillmyer, Marc

    2011-03-01

    Polylactide (PLA), a biodegradable polyester derived from plant sugars, is commercially available and used in a variety of applications ranging from serviceware to resorbable sutures. One limitation to diversifying the applications of the material is its inherent brittleness. Graft copolymers containing PLA arms and a rubbery aliphatic polymer backbone were synthesized by a combination of ring-opening metathesis and ring-opening transesterification polymerizations. The high degree of incompatibility between the arms and backbone resulted in microphase separation of the graft copolymer at increasingly low fractions of the backbone polymer, as evidenced by small-angle x-ray scattering. In graft copolymers with a rubbery content of only 5 wt percent, the tensile strain at break was observed to be as high as twenty times that of neat PLA. Studies are underway to provide insight into the critical polymer molecular parameters for enhanced toughness and the deformation mechanisms.

  13. Polymeric Carbon Dioxide

    SciTech Connect

    Yoo, C-S.

    1999-11-02

    Synthesis of polymeric carbon dioxide has long been of interest to many chemists and materials scientists. Very recently we discovered the polymeric phase of carbon dioxide (called CO{sub 2}-V) at high pressures and temperatures. Our optical and x-ray results indicate that CO{sub 2}-V is optically non-linear, generating the second harmonic of Nd: YLF laser at 527 nm and is also likely superhard similar to cubic-boron nitride or diamond. CO{sub 2}-V is made of CO{sub 4} tetrahedra, analogous to SiO{sub 2} polymorphs, and is quenchable at ambient temperature at pressures above 1 GPa. In this paper, we describe the pressure-induced polymerization of carbon dioxide together with the stability, structure, and mechanical and optical properties of polymeric CO{sub 2}-V. We also present some implications of polymeric CO{sub 2} for high-pressure chemistry and new materials synthesis.

  14. Nickel adsorption by sodium polyacrylate-grafted activated carbon.

    PubMed

    Ewecharoen, A; Thiravetyan, P; Wendel, E; Bertagnolli, H

    2009-11-15

    A novel sodium polyacrylate grafted activated carbon was produced by using gamma radiation to increase the number of functional groups on the surface. After irradiation the capacity for nickel adsorption was studied and found to have increased from 44.1 to 55.7 mg g(-1). X-ray absorption spectroscopy showed that the adsorbed nickel on activated carbon and irradiation-grafted activated carbon was coordinated with 6 oxygen atoms at 2.04-2.06 A. It is proposed that this grafting technique could be applied to other adsorbents to increase the efficiency of metal adsorption. PMID:19576692

  15. PREFACE: IUMRS-ICA 2008 Symposium, Sessions 'X. Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' and 'Y. Frontier of Polymeric Nano-Soft-Materials - Precision Polymer Synthesis, Self-assembling and Their Functionalization'

    NASA Astrophysics Data System (ADS)

    Takahara, Atsushi; Kawahara, Seiichi

    2009-09-01

    Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science (Symposium X of IUMRS-ICA2008) Toshiji Kanaya, Kohji Tashiro, Kazuo Sakura Keiji Tanaka, Sono Sasaki, Naoya Torikai, Moonhor Ree, Kookheon Char, Charles C Han, Atsushi Takahara This volume contains peer-reviewed invited and contributed papers that were presented in Symposium X 'Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' at the IUMRS International Conference in Asia 2008 (IUMRS-ICA 2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. Structure analyses of soft materials based on synchrotron radiation (SR) and neutron beam have been developed steadily. Small-angle scattering and wide-angle diffraction techniques clarified the higher-order structure as well as time dependence of structure development such as crystallization and microphase-separation. On the other hand, reflectivity, grazing-incidence scattering and diffraction techniques revealed the surface and interface structural features of soft materials. From the viewpoint of strong interests on the development of SR and neutron beam techniques for soft materials, the objective of this symposium is to provide an interdisciplinary forum for the discussion of recent advances in research, development, and applications of SR and neutron beams to soft matter science. In this symposium, 21 oral papers containing 16 invited papers and 14 poster papers from China, India, Korea, Taiwan, and Japan were presented during the three-day symposium. As a result of the review of poster and oral presentations of young scientists by symposium chairs, Dr Kummetha Raghunatha Reddy (Toyota Technological Institute) received the IUMRS-ICA 2008 Young Researcher Award. We are grateful to all invited speakers and many participants for valuable contributions and active discussions. Organizing committee of Symposium (IUMRS-ICA 2008) Professor Toshiji Kanaya (Kyoto University) Professor Kohji

  16. Cyclic Graft Copolymer Unimolecular Micelles: Effects of Cyclization on Particle Morphology and Thermoresponsive Behavior

    PubMed Central

    2016-01-01

    The synthesis of cyclic amphiphilic graft copolymers with a hydrophobic polycarbonate backbone and hydrophilic poly(N-acryloylmorpholine) (PNAM) side arms via a combination of ring-opening polymerization (ROP), cyclization via copper-catalyzed azide–alkyne cycloaddition (CuAAC), and reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. The ability of these cyclic graft copolymers to form unimolecular micelles in water is explored using a combination of light scattering, small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryoTEM) analyses, where particle size was found to increase with increasing PNAM arm length. Further analysis revealed differences in the solution conformations, loading capabilities, and morphologies of the cyclic graft copolymers in comparison to equivalent linear graft copolymer unimolecular micelle analogues. Furthermore, the cyclic and linear graft copolymers were found to exhibit significantly different cloud point temperatures. This study highlights how subtle changes in polymer architecture (linear graft copolymer versus cyclic graft copolymer) can dramatically influence a polymer’s nanostructure and its properties. PMID:27175037

  17. Immobilization of Polymeric Luminophor on Nanoparticles Surface.

    PubMed

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-12-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor. PMID:27090657

  18. Accompanying of parameters of color, gloss and hardness on polymeric films coated with pigmented inks cured by different radiation doses of ultraviolet light

    NASA Astrophysics Data System (ADS)

    Bardi, Marcelo Augusto Gonçalves; Machado, Luci Diva Brocardo

    2012-09-01

    In the search for alternatives to traditional paint systems solvent-based, the curing process of polymer coatings by ultraviolet light (UV) has been widely studied and discussed, especially because of their high content of solids and null emission of VOC. In UV-curing technology, organic solvents are replaced by reactive diluents, such as monomers. This paper aims to investigate variations on color, gloss and hardness of print inks cured by different UV radiation doses. The ratio pigment/clear coating was kept constant. The clear coating presented higher average values for König hardness than pigmented ones, indicating that UV-light absorption has been reduced by the presence of pigments. Besides, they have indicated a slight variation in function of cure degree for the studied radiation doses range. The gloss loss related to UV light exposition allows inferring that some degradation occurred at the surface of print ink films.

  19. Treatment of oil in water emulsions by ceramic-supported polymeric membranes

    SciTech Connect

    Castro, R.P.; Cohen, Y.; Monbouquette, H.G.

    1994-12-31

    A novel membrane was developed by growing polymer chains from the surface of a porous ceramic support, resulting in a composite membrane which combines the mechanical properties of the inorganic membrane with the selective interactions of the polymer. The configuration of the grafted polymer brush layer is determined by solvent-polymer interactions, with a hydrophilic polymer being stretched away from the surface by aqueous solutions and collapsed against the surface by organic solvents. This behavior of the grafted chains provides Ceramic-Supported Polymeric (CSP) membranes with unique properties for certain water treatment applications. One application envisioned for these CSP membranes, in which the selectivity is influenced by interactions between the solvent and the grafted polymer, is the cross-flow filtration of an oil-in-water emulsion. In this case, a hydrophilic grafted Polyvinylpyrrolidone (PVP) brush layer expanded into the pore volume due to the affinity of the polymer for water. These extended grafted chains preferentially allow the passage of water over oil, producing a permeate stream with a lower total organic carbon content compared to an unmodified membrane. Another advantage of the CSP membrane is in reducing permeate flux decline believed to be caused by the adsorption of oil onto the membrane surface. For the PVP-modified CSP membrane, the grafted polymer alters the membrane surface character from hydrophobic to hydrophilic, reducing the tendency for oil adsorption. This phenomenon was demonstrated by comparison of permeate flow rate behavior for both unmodified and graft polymerized (CSP) membranes.

  20. Radiation curing of epoxies

    NASA Astrophysics Data System (ADS)

    Dickson, Lawrence W.; Singh, Ajit

    The literature on radiation polymerization of epoxy compounds has been reviewed to assess the potential use of radiation for curing these industrially important monomers. Chemical curing of epoxies may proceed by either cationic or anionic mechanisms depending on the nature of the curing agent, but most epoxies polymerize by cationic mechanisms under the influence of high-energy radiation. Radiation-induced cationic polymerization of epoxy compounds is inhibited by trace quantities of water because of proton transfer from the chain-propagating epoxy cation to water. Several different methods with potential for obtaining high molecular weight polymers by curing epoxies with high-energy radiation have been studied. Polymeric products with epoxy-like properties have been produced by radiation curing of epoxy oligomers with terminal acrylate groups and mixtures of epoxies with vinyl monomers. Both of these types of resin have good potential for industrial-scale curing by radiation treatment.

  1. Grafting Technique to Eliminate Rootstock Suckering of Grafted Tomatoes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable grafting has been proposed as a technique for avoiding disease problems in tomatoes in open field production. In this study we investigated the current use of grafting in an open field scenario and found a serious problem with the grafting techniques. In the Fall of 2007, commercially pr...

  2. Grafts for Ridge Preservation

    PubMed Central

    Jamjoom, Amal; Cohen, Robert E.

    2015-01-01

    Alveolar ridge bone resorption is a biologic phenomenon that occurs following tooth extraction and cannot be prevented. This paper reviews the vertical and horizontal ridge dimensional changes that are associated with tooth extraction. It also provides an overview of the advantages of ridge preservation as well as grafting materials. A Medline search among English language papers was performed in March 2015 using alveolar ridge preservation, ridge augmentation, and various graft types as search terms. Additional papers were considered following the preliminary review of the initial search that were relevant to alveolar ridge preservation. The literature suggests that ridge preservation methods and augmentation techniques are available to minimize and restore available bone. Numerous grafting materials, such as autografts, allografts, xenografts, and alloplasts, currently are used for ridge preservation. Other materials, such as growth factors, also can be used to enhance biologic outcome. PMID:26262646

  3. Alveolar bone grafting

    PubMed Central

    Lilja, Jan

    2009-01-01

    In patients with cleft lip and palate, bone grafting in the mixed dentition in the residual alveolar cleft has become a well-established procedure. The main advantages can be summarised as follows: stabilisation of the maxillary arch; facilitation of eruption of the canine and sometimes facilitation of the lateral incisor eruption; providing bony support to the teeth adjacent to the cleft; raising the alar base of the nose; facilitation of closure of an oro-nasal fistula; making it possible to insert a titanium fixture in the grafted site and to obtain favourable periodontal conditions of the teeth within and adjacent to the cleft. The timing of the ABG surgery take into consideration not only eruption of the canine but also that of the lateral incisor, if present. The best time for bone grafting surgery is when a thin shell of bone still covers the soon erupting lateral incisor or canine tooth close to the cleft. PMID:19884665

  4. Surface-grafted polymers from electrodeposited macroprecursors

    NASA Astrophysics Data System (ADS)

    Rellamas Tria, Maria Celeste

    The use of electrochemically deposited macroprecursors for tethering polymers onto conducting surfaces is presented. Specifically, anodic electropolymerization was used as a tool to electrodeposit the precursors on electrodes that mediated the grafting of polymers onto surfaces. With this approach, patterning of surface-grafted polymers was also made possible through selective electrodeposition of the conjugated polymer network of the macroprecursors. This approach was used to fabricate protein and cell-resistant poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMEMA) brushes on Au surfaces. A chain transfer agent (CTA) was electrodeposited on the Au surface that served as the macroprecursor for the subsequent surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMEMA). X-ray photoelectron spectroscopy (XPS) results showed the stability of the electrogenerated CTA under anodic conditions while successful brush growth was confirmed by surface techniques including XPS, ellipsometry, atomic force microscopy (AFM), and contact angle measurements. The PPEGMEMA-coated substrate exhibited protein and cell-repellant properties comparable to other reported PEG-functionalized surfaces. The proposed approach also yielded polymer-patterned surfaces as discussed in Chapters 3 and 4. An electroactive photocrosslinker was employed to facilitate the dual mode patterning of polystyrene (PS) on the surface by either electropatterning or photopatteming route. An electrodeposited CTA was also utilized to selectively grow surface-grafted PS on conducting regions of the substrate. Subsequent backfilling of nonconducting areas with a silane atom transfer radical polymerization (ATRP) initiator directed the growth of poly-N-isopropylacrylamide (PNIPAM) that produced a patterned binary polymer system. The patterns were successfully characterized by AFM and IR-imaging. Surface-grafted poly

  5. Polymerization catalyst system

    SciTech Connect

    Graves, V.

    1986-03-25

    This patent describes a catalyst system for polymerizing at least one alpha-olefin under conditions characteristic of Ziegler polymerization. This system consists of: 1. a supported polymerization catalyst or mixture of polymerization catalysts prepared under anhydrous conditions by the sequential steps of: (a) preparing a slurry of inert particulate porous support material; (b) adding to the slurry a solution of an organomagnesium compound; (c) adding to the slurry and reacting a solution of a zirconium halide compound, hafnium compound or mixtures thereof; (d) adding to the slurry and reacting a halogenator; (e) adding to the slurry and reacting a tetravalent titanium halide compound; and (f) recovering solid catalyst component; 2. an organoaluminum compound; and 3. a promotor of chlorinated hydrocarbons having one to 20 carbon atoms.

  6. Surface properties and reduced biofouling of graft-copolymers that possess oppositely charged groups.

    PubMed

    Herzberg, Moshe; Sweity, Amer; Brami, Matan; Kaufman, Yair; Freger, Viatcheslav; Oron, Gideon; Belfer, Sophia; Kasher, Roni

    2011-04-11

    Microbial biofilms and their components present a major obstacle for ensuring the long-term effectiveness of membrane processes. Graft polymerization on membrane surfaces, in general, and grafting with oppositely charged monomers, have been shown to reduce biofouling significantly. In this study, surface forces and macromolecular properties of graft copolymers that possess oppositely charged groups were related to their potent antibiofouling behavior. Graft polymerization was performed using the negatively charged 3-sulphopropyl methacrylate (SPM) and positively charged [2-(methacryloyloxy)ethyl]-trimethylammonium (MOETMA) monomers to yield a copolymer layer on polyvinylidene fluoride (PVDF) surface. Quartz crystal microbalance with dissipation monitoring (QCM-D) technology was used to monitor the reduced adsorption of extracellular polymeric substances (EPS) extracted from a membrane bioreactor (MBR) wastewater treatment facility. Complemented measurements of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy provided evaluation of the antifouling properties of the surface. Increase in water content in grafted layer exposed to 100 mM aqueous NaCl solution was observed by QCM-D. Therefore, the grafted copolymer layer is swelled in the presence of 100 mM NaCl because of reversing of polymer self-association by counterions. Force measurements by atomic force microscopy (AFM) showed an increased repulsion between a carboxylate-modified latex (CML) particle probe and a modified PVDF surface, especially in the presence of 100 mM NaCl. The hydration and swelling of the grafted polymer layer are shown to repel EPS and reduce their adsorption. Delineating the surface properties of antifouling grafted layers may lead to the design of novel antifouling surfaces. PMID:21361342

  7. Nanostructural surface engineering of grafted polymers on inorganic oxide substrates for membrane separations

    NASA Astrophysics Data System (ADS)

    Yoshida, Wayne Hiroshi

    Nanostructural engineering of inorganic substrates by free radical graft polymerization was studied with the goal of developing new membrane materials for pervaporation. Graft polymerization consisted of modification of surface hydroxyls with vinyl trimethoxysilane, followed by solution graft polymerization reaction using either vinyl acetate (VAc) or vinyl pyrrolidone (VP). The topology of the modified surfaces was studied by atomic force microscopy (AFM) on both atomically smooth silicon wafer substrates and microporous inorganic membrane supports in order to deduce the effects of modification on the nanostructural properties of the membrane. While unmodified wafers showed a root-mean-square (RMS) surface roughness of 0.21 +/- 0.03 nm, roughness increased to 3.15 +/- 0.23 nm upon silylation. Under poor solvent conditions (i.e., air), surfaces modified with higher poly(vinyl acetate) (PVAc) or poly(vinyl pyrrolidone) (PVP) polymer graft yields displayed lateral inhomogeneities in the polymer layer. Although RMS surface roughness was nearly identical (0.81--0.85 nm) for PVAc-modified surfaces grafted at different monomer concentrations, the skewness of the height distribution decreased from 2.22 to 0.78 as polymer graft yield increased from 0.8 to 3.5 mg/m2. The polymer-modified surfaces were used to create inorganic pervaporation membranes consisting of a single macromolecular separation layer formed by graft polymerization. PVAc grafted silica membranes (500A native pore size) were found selective for MTBE in the separation of 0.1--1% (v/v) MTBE from water, achieving MTBE enrichment factors as high as 371 at a permeate flux of 0.38 l/m2 hr and a Reynolds number of 6390; however, these membranes could not separate anhydrous organic mixtures. Pervaporative separation of methanol/MTBE mixtures was possible with PVAc and PVP-modified alumina supports of 50A native pore size, where the separation layer consisted of grafted polymer chains with estimated radius of

  8. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  9. Radical-Mediated Enzymatic Polymerizations.

    PubMed

    Zavada, Scott R; Battsengel, Tsatsral; Scott, Timothy F

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes--catalytic proteins--owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol-ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  10. Preparation, characterization, and utilization of electrodes coated with polymeric networks formed by gamma-radiation crosslinking. Final report, 1 August 1982-31 January 1987

    SciTech Connect

    Heineman, W.R.; Mark, J.E.

    1987-04-01

    The preparation, characterization, and application of electrodes with specific chemical properties that are imparted by surface modification with polymer networks are the long-range goals of this research. Networks that are formed by crosslinking with gamma radiation were evaluated with respect to swelling in aqueous solution, retention of polymer in the network, permeability, and the effect of radiation dosage on all of these properties through its control of crosslinking. Ionic water-soluble polymers such as polydiallyl dimethyl ammonium cholride, poly vinylbenzyl trimethyl ammonium chloride, ploystyrene sulfonic acid, sodium salt and polyacrylic acid, which would ordinarily dissolve from the electrode surface in aqueous solution unless crosslinked into a network, and several neutral polymers such as polyacrylonitrile, polyethyleneimine, polydimethylsiloxane and poly vinyl alcohol investigated. The covalent attachment of organic and inorganic redox mediators and enzymes to networks by gamma irradiation of a mixture of polymer and the agent have been investigated. Network-coated electrodes with the appropriate properties are being developed for specific applications that required a stable, easily fabricated, fouling-resistant, rapidly responding, sensitive, and selective electrode.

  11. Gradient Poly(styrene-co-polyglycidol) Grafts via Silicon Surface-Initiated AGET ATRP.

    PubMed

    Gosecka, Monika; Pietrasik, Joanna; Decorse, Philippe; Glebocki, Bartosz; Chehimi, Mohamed M; Slomkowski, Stanislaw; Basinska, Teresa

    2015-05-01

    Gradient copolymer grafts of styrene and α-tert-butoxy-ω-vinylbenzyl-poly(glycidol ethoxyethyl ether) (PGLet), a precursor of α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (PGL), were prepared on silicon wafers via a surface-initiated activator generated by electron transfer radical polymerization (AGET ATRP). Silicon plates with previously attached 2-bromoisobutyrate served as a macroinitiator for the AGET ATRP (activator generated by electron transfer) of styrene and PGLet. The copolymers' gradient P(S-co-PPGL) of composition and thickness was obtained by a simple method where the plates were slowly removed from reaction mixture using a step motor. PGLet was added continuously (dropwise) into the reactor during withdrawal of the plates from solution in order to increase the relative concentration of PGLet in polymerization mixture. A range of strategies of making grafts was tested. The plates with copolymers grafts were analyzed by various techniques, like XPS, ellipsometry, and FTIR spectroscopy. The results indicate that the AGET ATRP process is dependent on the styrene/PGLet macromonomer ratio in the polymerization mixture. Under optimal conditions, the addition of PGLet during polymerization and subsequent deprotection of hydroxyl groups of PGLet permit to obtain plates with a novel copolymer layer with composition, thickness, and wettability gradient. Plates with chemical composition of copolymer grafts gradient served as versatile supports with controlled hydrophilic/hydrophobic area and were suitable for tailored deposition of particles. PMID:25871942

  12. Impact of reaction conditions on architecture and rheological properties of starch graft polyacrylamide polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We carried out experiments examining the impact that solvent selection and reaction conditions have on the radical initiated graft polymerization reaction of acrylamide onto starch. We have also evaluated the rheological properties the starch graftpolyacrylamide product when a gel is formed in water...

  13. Skin grafting of the horse.

    PubMed

    Schumacher, J; Hanselka, D V

    1989-12-01

    Free autogenous skin grafting of the horse is indicated for wounds too large to heal by contraction and epithelization. Techniques of pinch, punch, tunnel, and sheet grafting are described. Allografting and storage of skin for delayed grafting are discussed. PMID:2691033

  14. Bone Grafts in Craniofacial Surgery

    PubMed Central

    Elsalanty, Mohammed E.; Genecov, David G.

    2009-01-01

    Reconstruction of cranial and maxillofacial defects is a challenging task. The standard reconstruction method has been bone grafting. In this review, we shall describe the biological principles of bone graft healing, as pertinent to craniofacial reconstruction. Different types and sources of bone grafts will be discussed, as well as new methods of bone defect reconstruction. PMID:22110806

  15. Synthesis and properties of silane-fluoroacrylate grafted starch.

    PubMed

    Qu, Jia; He, Ling

    2013-10-15

    The latex of silane-fluoroacrylate grafted starch for coating materials, VTMS-starch/P(MMA/BA/3FMA), is obtained by two step grafting reactions. Vinyltrimethoxysilane (VTMS) is primarily grafted onto starch by condensation between Si-OH and C-OH at 120 °C, and then the copolymer of methyl methacrylate (MMA), butyl acrylate (BA) and 2,2,2-trifluoroethyl methacrylate (3FMA) is grafted onto the VTMS-starch by emulsion polymerization. Fourier transform infrared spectrometry (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to confirm the chemically grafting reactions in every step. The conversion percent, grafting percent and grafting efficiency for VTMS-starch/p(MMA/BA/3FMA) latex indicate that the optimum conditions should be controlled at 75 °C for 1h as VTMS-starch/P(MMA/BA/3FMA) in 1/3 weight ratio. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analysis have revealed that the latexes exhibit the uniform spherical particles of 40-60 nm in a narrow size distribution. The latex films perform the obvious hydrophobic (107°) property, lower surface free energy (25-35 mN/m) and the higher thermostability (330-440 °C) than starch (51°, 51.32 mN/m, 100-330 °C). Dynamic thermomechanical analysis (DMA) shows that the latex film could gain considerable toughness and strength with an elongation at break of 39.45% and a tensile strength of 11.97 MPa. PMID:23987447

  16. Tunable Pickering emulsions with polymer-grafted lignin nanoparticles (PGLNs).

    PubMed

    Silmore, Kevin S; Gupta, Chetali; Washburn, Newell R

    2016-03-15

    activities, and polymer-nanoparticle interactions are critical for optimizing interfacial activities. Controlled radical polymerization is a powerful tool for polymer grafting that can leverage the intrinsic interfacial functions of lignin for the formation of Pickering emulsions. PMID:26707776

  17. Synthesis and characterization of tannin grafted polycaprolactone.

    PubMed

    Song, Ping; Jiang, Suchen; Ren, Yajun; Zhang, Xue; Qiao, Tiankui; Song, Xiaofeng; Liu, Qimin; Chen, Xuesi

    2016-10-01

    Tannin and biodegradable polyester have attracted increasing interest for biomedical applications. To improve their compatibility, a novel tannin grafted polycaprolactone (TA-g-PCL) has been synthesized via ring-opening polymerization reaction. The structure of the product is characterized with FTIR, (1)H NMR and GPC. GPC results show that the experimental molecular weight is far less than the theoretical due to complicated stereo structure and large steric hindrance of tannic molecule, but the polydispersity of the product is narrow. At 115.76:1 of molar ratio of CL to tannin, molecular weight of the product reaches the maximum. Thermodynamics properties and dissolubility of TA-g-PCL are closely related to its molecular weight. With PCL molecular chain grows, TA-g-PCL changes from amorphous form to crystalline structure, and its dissolubility in chloroform is also enhanced significantly. PMID:27388129

  18. Grafting for disease resistance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The primary purpose of grafting vegetables worldwide has been to provide resistance to soil-borne diseases. The potential loss of methyl bromide as a soil fumigant combined with pathogen resistance to commonly used pesticides will make resistance to soil-borne pathogens even more important in the fu...

  19. Acrylonitrile grafted to PVDF

    SciTech Connect

    Yang, Jin; Eitouni, Hany Basam

    2015-03-31

    PVDF-g-PAN has been synthesized by grafting polyacrylonitrile onto polyvinylidene fluoride using an ATRP/AGET method. The novel polymer is ionically conducive and has much more flexibility than PVDF alone, making it especially useful either as a binder in battery cell electrodes or as a polymer electrolyte in a battery cell.

  20. Mixing in polymeric microfluidic devices.

    SciTech Connect

    Schunk, Peter Randall; Sun, Amy Cha-Tien; Davis, Robert H.; Brotherton, Christopher M. (University of Colorado at Boulder, Boulder, CO)

    2006-04-01

    This SAND report describes progress made during a Sandia National Laboratories sponsored graduate fellowship. The fellowship was funded through an LDRD proposal. The goal of this project is development and characterization of mixing strategies for polymeric microfluidic devices. The mixing strategies under investigation include electroosmotic flow focusing, hydrodynamic focusing, physical constrictions and porous polymer monoliths. For electroosmotic flow focusing, simulations were performed to determine the effect of electroosmotic flow in a microchannel with heterogeneous surface potential. The heterogeneous surface potential caused recirculations to form within the microchannel. These recirculations could then be used to restrict two mixing streams and reduce the characteristic diffusion length. Maximum mixing occurred when the ratio of the mixing region surface potential to the average channel surface potential was made large in magnitude and negative in sign, and when the ratio of the characteristic convection time to the characteristic diffusion time was minimized. Based on these results, experiments were performed to evaluate the manipulation of surface potential using living-radical photopolymerization. The material chosen to manipulate typically exhibits a negative surface potential. Using living-radical surface grafting, a positive surface potential was produced using 2-(Dimethylamino)ethyl methacrylate and a neutral surface was produced using a poly(ethylene glycol) surface graft. Simulations investigating hydrodynamic focusing were also performed. For this technique, mixing is enhanced by using a tertiary fluid stream to constrict the two mixing streams and reduce the characteristic diffusion length. Maximum mixing occurred when the ratio of the tertiary flow stream flow-rate to the mixing streams flow-rate was maximized. Also, like the electroosmotic focusing mixer, mixing was also maximized when the ratio of the characteristic convection time to the

  1. Grafting sulfobetaine monomer onto the segmented poly(ether-urethane) surface to improve hemocompatibility.

    PubMed

    Yuan, Y L; Ai, F; Zhang, J; Zang, X B; Shen, J; Lin, S C

    2002-01-01

    Polyurethanes are widely used as blood-contacting biomaterials, due to their good biocompatibility and mechanical properties. Nevertheless, their blood compatibility is still not adequate for more demanding applications. Surface modification is an effective way to improve the hemocompatibility for biomaterials. The purpose of the present study was to synthesize a novel nonthrombogenic biomaterial by modifying the surface of polyurethane. Ozonization was used to introduce active peroxide groups onto the segmented poly(ether-urethane) (SPEU) film surface and graft polymerization of N,N'-dimethyl (methacryloyloxyethyl) ammonium propanesulfonate (DMAPS), a sulfobetaine structure, onto the ozone-activated SPEU surface was conducted. The SPEU-g-PDMAPS film was characterized by ATR-FTIR, XPS, and contact angle measurements. ATR-FTIR and XPS confirmed the graft polymerization. The grafted film possessed a relatively hydrophilic surface, as revealed by contact angle measurement. The blood compatibility of the grafted films was evaluated by a platelet-rich plasma (PRP) adhesion study and scanning electron microscopy, using SPEU film as the reference. No platelet adhesion was observed for the grafted films incubated with PRP at 37 degrees C for 60 and 180 min. This new sulfobetaine structure grafted biomaterial might have potential for biomedical applications. PMID:12484485

  2. Preparation and Characterization of Cotton Textile Graft Copolymers as Cation Exchanger

    NASA Astrophysics Data System (ADS)

    Mostafa, Kh. M.

    2005-03-01

    Acrylic Acid (AA) was graft copolymerized with cotton cellulose in fabric form to prepare poly (AA)-cotton graft copolymer cation exchanger using Fe2+/BrO3- redox system in aqueous medium under a nitrogen atmosphere. The effect of Fe2+, BrO3- and monomer concentrations, pH as well as time and temperature of polymerization were studied by determining the grafting parameters gravimetrically, like Graft Yield (GY %) and Graft Reaction Efficiency (GRE %). On the other hand, the newly prepared poly (AA)-cotton graft copolymers were characterized for different heavy metals ions removal to determined their suitability as cation exchanger. On the basis of a detailed investigation of the above factors, the appropriate conditions for grafting were as follows: Fe2+, 0.005 mol L-1; BrO3-, 0.001 mol L-1; pH, 2; monomer, (50% based on weight of substrate); time, 90 min and temperature, 35°C. On the other hand, the potential value of the newly prepared poly (AA)-cotton graft copolymer to serve as cation exchanger was assessed through measurements of critical properties such as removal of different heavy metal ions from their solutions as well as durability.

  3. Bone grafts and their substitutes.

    PubMed

    Fillingham, Y; Jacobs, J

    2016-01-01

    The continual cycle of bone formation and resorption is carried out by osteoblasts, osteocytes, and osteoclasts under the direction of the bone-signaling pathway. In certain situations the host cycle of bone repair is insufficient and requires the assistance of bone grafts and their substitutes. The fundamental properties of a bone graft are osteoconduction, osteoinduction, osteogenesis, and structural support. Options for bone grafting include autogenous and allograft bone and the various isolated or combined substitutes of calcium sulphate, calcium phosphate, tricalcium phosphate, and coralline hydroxyapatite. Not all bone grafts will have the same properties. As a result, understanding the requirements of the clinical situation and specific properties of the various types of bone grafts is necessary to identify the ideal graft. We present a review of the bone repair process and properties of bone grafts and their substitutes to help guide the clinician in the decision making process. PMID:26733632

  4. Injectable polyHIPEs as high-porosity bone grafts.

    PubMed

    Moglia, Robert S; Holm, Jennifer L; Sears, Nicholas A; Wilson, Caitlin J; Harrison, Dawn M; Cosgriff-Hernandez, Elizabeth

    2011-10-10

    Polymerization of high internal phase emulsions (polyHIPEs) is a relatively new method for the production of high-porosity scaffolds. The tunable architecture of these polyHIPE foams makes them attractive candidates for tissue engineered bone grafts. Previously studied polyHIPE systems require either toxic diluents or high cure temperatures which prohibit their use as an injectable bone graft. In contrast, we have developed an injectable polyHIPE that cures at physiological temperatures to a rigid, high-porosity foam. First, a biodegradable macromer, propylene fumarate dimethacrylate (PFDMA), was synthesized that has appropriate viscosity and hydrophobicity for emulsification. The process of surfactant selection is detailed with particular focus on the key structural features of both polymer (logP values, hydrogen bond acceptor sites) and surfactant (HLB values, hydrogen bond donor sites) that enable stable HIPE formation. Incubation of HIPEs at 37 °C was used to initiate radical cross-linking of the unsaturated double bond of the methacrylate groups to polymerize the continuous phase and lock in the emulsion geometry. The resulting polyHIPEs exhibited ~75% porosity, pore sizes ranging from 4 to 29 μm, and an average compressive modulus and strength of 33 and 5 MPa, respectively. These findings highlight the great potential of these scaffolds as injectable, tissue engineered bone grafts. PMID:21861465

  5. Injectable PolyHIPEs as High Porosity Bone Grafts

    PubMed Central

    Moglia, Robert S.; Holm, Jennifer L.; Sears, Nicholas A.; Wilson, Caitlin J.; Harrison, Dawn M.; Cosgriff-Hernandez, Elizabeth

    2011-01-01

    Polymerization of high internal phase emulsions (polyHIPEs) is a relatively new method for the production of high porosity scaffolds. The tunable architecture of these polyHIPE foams make them attractive candidates for tissue engineered bone grafts. Previously studied polyHIPE systems require either toxic diluents or high cure temperatures which prohibit their use as an injectable bone graft. In contrast, we have developed an injectable polyHIPE that cures at physiological temperatures to a rigid, high-porosity foam. First, a biodegradable macromer, propylene fumarate dimethacrylate (PFDMA), was synthesized that has appropriate viscosity and hydrophobicity for emulsification. The process of surfactant selection is detailed with particular focus on the key structural features of both polymer (log P values, hydrogen bond acceptor sites) and surfactant (HLB values, hydrogen bond donor sites) that enable stable HIPE formation. Incubation of HIPEs at 37°C was used to initiate radical crosslinking of the unsaturated double bond of the methacrylate groups to polymerize the continuous phase and lock in the emulsion geometry. The resulting polyHIPEs exhibited ~75% porosity, pore sizes ranging from 4 to 29 μm, and an average compressive modulus and strength of 33 and 5 MPa, respectively. These findings highlight the great potential of these scaffolds as injectable, tissue engineered bone grafts. PMID:21861465

  6. Synthesis of polyolefin graft copolymers by borane approach

    SciTech Connect

    Jiang, G.J.; Rhubright, D.; Bernard, R.L.; Chung, T.C.

    1993-12-31

    This paper summarizes the new developments in the graft reaction of polyolefin by borane approach. It is becoming clear that the borane groups in polyolefins are valuable intermediates which not only can be quantitatively converted to a wide range of functional groups but also can be used as initiator or co-initiator for cationic or free radical polymerizations. Some interesting graft polymers, such as PP-g-PMMA, PP-g-PVA, PP-g-polycapolactone, EP-g-PMMA, and Butyl-g-PMMA, have been synthesized with controllable compositions and molecular microstructures. Most of them would be otherwise very difficult to prepare by the other existing methods. Several methods have been developed to incorporate borane groups to polyolefins, including both direct and post polymerizations. One unique feature of borane group is its excellent stability to transition metal catalysts, such as Ziegler-Natta, and good solubility in hydrocarbon solvents. These offer the possibility to prepare borane containing polyolefins with a broad range of copolymer composition and microstructure. In terms of application, graft copolymers are useful interfacial reagents in polyolefin blends and composites.

  7. Silicon tetrachloride plasma induced grafting for starch-based composites

    NASA Astrophysics Data System (ADS)

    Ma, Yonghui C.

    Non-modified virgin starch is seldom used directly in industrial applications. Instead, it is often physically and/or chemically modified to achieve certain enhanced properties. For many of the non-food applications, these modifications involve changing its hydrophilicity to create hydrophobic starch. In this study, the hydrophobic starch was produced through silicon tetrachloride (SiCl4) plasma induced graft polymerization, so that it could be used as a renewable and biodegradable component of, or substitute for, the petrochemical-based plastics. It was suggested that this starch graft-copolymer might be used as reinforcing components in silicone-rubber materials for starch-based composites. To make this starch graft-copolymer, the ethyl ether-extracted starch powders were surface functionalized by SiCl4 plasma using a 13.56 MHz radio frequency rotating plasma reactor and subsequently stabilized by either ethylene diamine or dichlorodimethylsilane (DCDMS). The functionalized starch was then graft-polymerized with DCDMS to form polydimethylsiloxane (PDMS) layers around the starch granules. The presence of this PDMS layer was demonstrated by electron spectroscopy for chemical analysis (ESCA/XPS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), gas chromatography-mass spectroscopy (GC-MS), thermo gravimetry/differential thermal analysis (TG/DTA), and other analyses. It was shown that the surface morphology, thermal properties, swelling characteristic, and hydrophilicity of starch were all changed due to the existence of this protective hydrophobic PDMS layer. Several different procedures to carry out the functionalization and graft polymerization steps were evaluated to improve the effectiveness of the reactions and to prevent the samples from being hydrolyzed by the grafting byproduct HCl. Actinometry, GC-MS, and residual gas analyzer (RGA) were used to investigate the mechanisms of the SiCl4 discharge and to optimize the plasma

  8. INHIBITING THE POLYMERIZATION OF NUCLEAR COOLANTS

    DOEpatents

    Colichman, E.L.

    1959-10-20

    >The formation of new reactor coolants which contain an additive tbat suppresses polymerization of the primary dissoclation free radical products of the pyrolytic and radiation decomposition of the organic coolants is described. The coolants consist of polyphenyls and condensed ring compounds having from two to about four carbon rings and from 0.1 to 5% of a powdered metal hydride chosen from the group consisting of the group IIA and IVA dispersed in the hydrocarbon.

  9. Anticoagulant surface of 316 L stainless steel modified by surface-initiated atom transfer radical polymerization.

    PubMed

    Guo, Weihua; Zhu, Jian; Cheng, Zhenping; Zhang, Zhengbiao; Zhu, Xiulin

    2011-05-01

    Polished 316 L stainless steel (SS) was first treated with air plasma to enhance surface hydrophilicity and was subsequently allowed to react with 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane to introduce an atom transfer radical polymerization (ATRP) initiator. Accordingly, the surface-initiated atom transfer radical polymerization of polyethylene glycol methacrylate (PEGMA) was carried out on the surface of the modified SS. The grafting progress was monitored by water contact angle measurements, X-ray photoelectron spectroscopy and atomic force microscopy. The polymer thickness as a function different polymerization times was characterized using a step profiler. The anticoagulative properties of the PEGMA modified SS surface were investigated. The results showed enhanced anticoagulative to acid-citrate-dextrose (ACD) blood after grafting PEGMA on the SS surface. PMID:21528878

  10. Organocatalyzed Group Transfer Polymerization.

    PubMed

    Chen, Yougen; Kakuchi, Toyoji

    2016-08-01

    In contrast to the conventional group transfer polymerization (GTP) using a catalyst of either an anionic nucleophile or a transition-metal compound, the organocatalyzed GTP has to a great extent improved the living characteristics of the polymerization from the viewpoints of synthesizing structurally well-defined acrylic polymers and constructing defect-free polymer architectures. In this article, we describe the organocatalyzed GTP from a relatively personal perspective to provide our colleagues with a perspicuous and systematic overview on its recent progress as well as a reply to the curiosity of how excellently the organocatalysts have performed in this field. The stated perspectives of this review mainly cover five aspects, in terms of the assessment of the livingness of the polymerization, limit and scope of applicable monomers, mechanistic studies, control of the polymer structure, and a new GTP methodology involving the use of tris(pentafluorophenyl)borane and hydrosilane. PMID:27427399

  11. Synthesis and characterization of nanocomposite organic/inorganic hybrid materials using living cationic polymerization

    NASA Astrophysics Data System (ADS)

    Kim, Iljin

    A series of novel chlorosilyl functional initiators have been prepared and applied for the first time in the living cationic polymerization of isobutylene (IB). Well-defined polyisobutylenes (PIBs) carrying mono-, di-, and trichlorosilyl head-group, and a tert-chloro end-group were synthesized using newly designed silyl-functional initiators in conjunction with TiCl4 in Hex:MeCl (60:40, v:v) at -80°C. End-group analysis by 1H NMR spectroscopy verified the product structure and the survival of the Si-Cl head-groups during the polymerization. The chlorosilyl functional initiators and chlorosilyl functional PIBs have been employed for the synthesis of PIB brushes on planar silicate substrates by the "grafting from" and "grafting to" techniques. Structurally well-defined polymer/inorganic nanocomposites were prepared by surface-initiated living cationic polymerization of isobutylene (IB). The living cationic polymerization of IB was initiated from initiators self-assembled on the surface of silica nanoparticles in the presence of additional soluble "free initiator" with TiCl4 in hexanes/CH3Cl (60/40, v/v) at -80°C. The polymerization displayed the diagnostic criteria for living cationic polymerization and provided densely grafted polymers of controlled molecular weight with an approximate graft density of 3.3 chains/nm 2. The surface-initiated polymerization of IB without added "free initiator" also yielded grafted polymer chains with good molecular weight control and narrow molecular weight distribution (Mw/M n). A series of novel hybrid poly(styryl-POSS), poly(isobutylene- b-(styryl-POSS)), and poly(isobutylene-b-(styryl-POSS)- b-isobutylene) are synthesized and characterized. Living cationic polymerization of styryl-POSS macromer was carried out using the 1-chloro-1-(4-methyphenyl)ethane (p-MeStCl)/TiCl4/MeChx:CH3Cl (60:40, v:v)/-80°C system in the presence of DTBP. Using these conditions, we have synthesized AB diblock, and ABA linear triblock copolymers

  12. Plasma polymerized high energy density dielectric films for capacitors

    NASA Technical Reports Server (NTRS)

    Yamagishi, F. G.

    1983-01-01

    High energy density polymeric dielectric films were prepared by plasma polymerization of a variety of gaseous monomers. This technique gives thin, reproducible, pinhole free, conformable, adherent, and insoluble coatings and overcomes the processing problems found in the preparation of thin films with bulk polymers. Thus, devices are prepared completely in a vacuum environment. The plasma polymerized films prepared all showed dielectric strengths of greater than 1000 kV/cm and in some cases values of greater than 4000 kV/cm were observed. The dielectric loss of all films was generally less than 1% at frequencies below 10 kHz, but this value increased at higher frequencies. All films were self healing. The dielectric strength was a function of the polymerization technique, whereas the dielectric constant varied with the structure of the starting material. Because of the thin films used (thickness in the submicron range) surface smoothness of the metal electrodes was found to be critical in obtaining high dielectric strengths. High dielectric strength graft copolymers were also prepared. Plasma polymerized ethane was found to be thermally stable up to 150 C in the presence of air and 250 C in the absence of air. No glass transitions were observed for this material.

  13. Thermally and photoinduced polymerization of ultrathin sexithiophene films

    SciTech Connect

    Sander, Anke; Hammer, Rene; Duncker, Klaus; Förster, Stefan; Widdra, Wolf

    2014-09-14

    The thermally-induced polymerization of α-sexithiophene (6T) molecules on Ag(001) and Au(001) gives rise to long unbranched polymer chains or branched polymer networks depending on the annealing parameters. There, the onset temperature for polymerization depends on the strength of interaction with the underlying substrate. Similar polymerization processes are also induced by ultraviolet radiation with photon energies between 3.0 and 4.2 eV. Radical formation by an electronic excitation in the 6T molecule is proposed as the driving mechanism that necessitates the interplay with the metallic substrate.

  14. Preparation and characterization of optical-functional diblock copolymer brushes on hollow sphere surface via atom transfer radical polymerization

    SciTech Connect

    Wang, Li-Ping; Li, Wen-Zhi; Zhao, Li-Min; Zhang, Chun-Juan; Wang, Yan-Dong; Kong, Li-Li; Li, Ling-Ling

    2010-09-15

    The optical-functional poly(methyl methacrylate)-block-Tb complex diblock copolymer brushes grafted from hollow sphere surface via atom transfer radical polymerization were investigated in this work. A sufficient amount of azo initiator was introduced onto hollow sphere surface firstly. Then the monomer methyl methacrylate was polymerized via surface-initiated reverse atom transfer radical polymerization using azo group modified hollow sphere as initiator. Following, the poly(methyl methacrylate) modified hollow sphere was used as maroinitiator for surface-initiated atom transfer radical polymerization of Tb complex. The samples were characterized by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, gel permeation chromatographer and transmission electron microscopy, respectively. The results indicated that the poly(methyl methacrylate) had grafted from hollow sphere surface and the average diameter of hollow core was about 1 {mu}m. The optical properties of the poly(methyl methacrylate)-block-Tb copolymer modified hollow sphere were also reported.

  15. Copolymer Synthesis and Characterization by Post-Polymerization Modification

    NASA Astrophysics Data System (ADS)

    Galvin, Casey James

    This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in

  16. Dead Sea Minerals loaded polymeric nanoparticles.

    PubMed

    Dessy, Alberto; Kubowicz, Stephan; Alderighi, Michele; Bartoli, Cristina; Piras, Anna Maria; Schmid, Ruth; Chiellini, Federica

    2011-10-15

    Therapeutic properties of Dead Sea Water (DSW) in the treatment of skin diseases such as atopic dermatitis, psoriasis and photo aging UV damaged skin have been well established. DSW is in fact rich in minerals such as calcium, magnesium, sodium, potassium, zinc and strontium which are known to exploit anti-inflammatory effects and to promote skin barrier recovery. In order to develop a Dead Sea Minerals (DSM) based drug delivery system for topical therapy of skin diseases, polymeric nanoparticles based on Poly (maleic anhydride-alt-butyl vinyl ether) 5% grafted with monomethoxy poly(ethyleneglycol) 2000 MW (PEG) and 95% grafted with 2-methoxyethanol (VAM41-PEG) loaded with DSM were prepared by means of a combined miniemulsion/solvent evaporation process. The resulting nanoparticles were characterized in terms of dimension, morphology, biocompatibility, salt content and release. Cytocompatible spherical nanoparticles possessing an average diameter of about 300 nm, a time controlled drug release profile and a high formulation yield were obtained. PMID:21676600

  17. Siloxane-grafted membranes

    DOEpatents

    Friesen, Dwayne T.; Obligin, Alan S.

    1989-01-01

    Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional groups. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.

  18. Siloxane-grafted membranes

    DOEpatents

    Friesen, D.T.; Obligin, A.S.

    1989-10-31

    Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional group. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.

  19. Preparation and characterization of poly(isobutyl methacrylate) microbeads with grafted amidoxime groups

    NASA Astrophysics Data System (ADS)

    Çaykara, Tuncer; Alaslan, Şerife Şirin; Gürü, Metin; Bodugöz, Hatice; Güven, Olgun

    2007-10-01

    Poly(isobutyl methacrylate) (PiBMA) microspheres with a 800- to 1500-μm diameter range synthesized by suspension polymerization technique were used as the trunk polymer in the preparation of a highly efficient new adsorbent. Glycidyl methacrylate (GMA) was grafted onto the trunk polymer by pre-irradiation grafting technique. Grafting conditions were optimized, and GMA grafted PiBMA beads were modified with iminodiacetonitrile (IDAN) in ethanol at 80 °C. The nitrile groups were then amidoximated by using 6% (m/v) hydroxylamine hydrochloride in methanol solution. The IDAN modification and the conversion of the nitrile groups to amidoxime were followed by FT-IR spectroscopy. The surface morphology and thermal behavior of the PiBMA and its modificated forms were also characterized by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques further confirming modification and amidoximation.

  20. Variable Effect during Polymerization

    ERIC Educational Resources Information Center

    Lunsford, S. K.

    2005-01-01

    An experiment performing the polymerization of 3-methylthiophene(P-3MT) onto the conditions for the selective electrode to determine the catechol by using cyclic voltammetry was performed. The P-3MT formed under optimized conditions improved electrochemical reversibility, selectivity and reproducibility for the detection of the catechol.

  1. Polymerized and functionalized triglycerides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  2. Programmable Supramolecular Polymerizations.

    PubMed

    van der Zwaag, Daan; de Greef, Tom F A; Meijer, E W

    2015-07-13

    Living large: Rational design of self-assembly pathways has been demonstrated in supramolecular polymers. By controlling the concentration of an aggregation-competent monomer through intramolecular interactions, living supramolecular polymerization conditions were achieved. This universal approach can be used to obtain aggregates of well-defined length and narrow dispersity, and allows access to new supramolecular polymer architectures. PMID:26095705

  3. Effective integrative supramolecular polymerization.

    PubMed

    Zhang, Qiwei; Tian, He

    2014-09-26

    Exercise control: By taking advantage of self-sorting processes among host-guest components, a controlled supramolecular polymerization can be realized, as demonstrated recently with the preparation of a cucurbit[n]uril-based supramolecular polymer. This method may be used for the design of more ordered supramolecular polymers from complex and discrete components. PMID:25080388

  4. Protein specific polymeric immunomicrospheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1980-01-01

    Small, round, bio-compatible microspheres capable of covalently bonding proteins and having a uniform diameter below about 3500 A are prepared by substantially instantaneously initiating polymerization of an aqueous emulsion containing no more than 35% total monomer including an acrylic monomer substituted with a covalently bondable group such as hydroxyl, amino or carboxyl and a minor amount of a cross-linking agent.

  5. Behavior of grafted polymers on nanofillers and their influence on polymer nanocomposite properties

    NASA Astrophysics Data System (ADS)

    Dukes, Douglas Michael

    Polymer nanocomposites continue to receive wide-spread acclaim for their potential to improve composite materials beyond conventional macroscale fillers. The improvement lies both in the altered properties of the particle itself and in the interaction region surrounding the filler. As the surface area of the filler increases, a greater volume fraction of this interphase region is present in the composite. However, simply minimizing the particle size to maximize surface area introduces additional problems; the larger specific surface area promotes aggregation to reduce the surface energy. Since the composite's properties are largely tied to the morphology, aggregation prevents control over the dispersion state of the filler, and thus the properties. Therefore, disaggregation and morphology control are vital to achieving designable nanocomposites. To accomplish both tasks, this thesis focuses on the behavior of grafted polymer coatings on nanoparticles and their in uence on the macroscopic properties. Grafted chains play an integral role in both morphology control and reinforcement. To investigate the behavior of polymer brushes on nanoparticles, polystyrene was grafted on 15 nm silica particles at varying graft densities and molecular weights. Dynamic light scattering studies in dilute solution were performed to obtain the brush height as a function of both graft density and molecular weight. Three distinct regimes of behavior exist, the "mushroom", the semi-dilute polymer brush (SDPB), and the concentrated polymer brush (CPB) regimes. In the CPB regime, which is an extraordinary configuration of highly-stretched chains on densely grafted surfaces, the brush height h was found to scale as h ∝ N4/5, where N is the degree of polymerization. This result is contrary to the observed scaling of the CPB in flat interface systems, where h ∝ N1. To explore the behavior of grafted chains in the melt, molecular dynamics simulations were performed on grafted nanoparticles

  6. [Bone grafts in orthopedic surgery].

    PubMed

    Zárate-Kalfópulos, Barón; Reyes-Sánchez, Alejandro

    2006-01-01

    In orthopedic surgery the demand for the use of bone grafts increases daily because of the increasing quantity and complexity of surgical procedures. At present, the gold standard is the autologous bone graft but the failure rate, morbidity of the donor site and limited availability have stimulated a proliferation for finding materials that work as bone graft substitutes. In order to have good success, we must know the different properties of these choices and the environment where the graft is going to be used. As bone graft substitutes and growth factors become clinical realities, a new gold standard will be defined. Tissue engineering and gene therapy techniques have the objective to create an optimum bone graft substitute with a combination of substances with properties of osteconduction, osteogenesis and osteoinduction. PMID:16875525

  7. Surface Grafted Polysarcosine as a Peptoid Antifouling Polymer Brush

    PubMed Central

    Lau, King Hang Aaron; Ren, Chunlai; Sileika, Tadas S.; Park, Sung Hyun; Szleifer, Igal; Messersmith, Phillip B.

    2012-01-01

    Poly(N-substituted glycine) “peptoids” are a class of peptidomimetic molecules receiving significant interest as engineered biomolecules. Sarcosine (i.e. poly(N-methyl glycine)) has the simplest sidechain chemical structure of this family. In this contribution, we demonstrate that surface-grafted polysarcosine (PSAR) brushes exhibit excellent resistance to non-specific protein adsorption and cell attachment. Polysarcosine was coupled to a mussel adhesive protein inspired DOPA-Lys pentapeptide, which enabled solution grafting and control of the surface chain density of the PSAR brushes. Protein adsorption was found to decrease monotonically with increasing grafted chain densities, and protein adsorption could be completely inhibited above certain critical chain densities specific to different polysarcosine chain-lengths. The dependence of protein adsorption on chain length and density was also investigated by a molecular theory. PSAR brushes at high chain length and density were shown to resist fibroblast cell attachment over a 7 wk period, as well as resist the attachment of some clinically relevant bacteria strains. The excellent antifouling performance of PSAR may be related to the highly hydrophilic character of polysarcosine, which was evident from high-pressure liquid chromatography measurements of polysarcosine and water contact angle measurements of the PSAR brushes. Peptoids have been shown to resist proteolytic degradation and polysarcosine could be produced in large quantities by N-carboxy anhydride polymerization. In summary, surface grafted polysarcosine peptoid brushes hold great promise for antifouling applications. PMID:23101930

  8. Ibuprofen microencapsulation within acrylamide-grafted chitosan and methylcellulose interpenetrating polymer network microspheres: Synthesis, characterization, and release studies.

    PubMed

    Bulut, Emine

    2016-06-01

    This study deals with the development of interpenetrating polymer network (IPN) microspheres of acrylamide (AAm) grafted onto a chitosan (CS) backbone and methylcellulose (MC). Chitosan-graft-polyacrylamide (CS-g-PAAm) was synthesized by cerium (IV) ammonium nitrate-induced free radical graft polymerization. The grafting percentage was found to be 50.58%. The synthesized graft copolymer and MC were used to prepare microspheres by the water-in-oil (w/o) emulsion-crosslinking method, and crosslinked with glutaraldehyde (GA) as drug delivery matrices of ibuprofen (IBU). The release of IBU from microspheres decreased when the amount of CS-g-PAAm in the polymer matrix and amount of crosslinker added were increased, while it increased with the increase of the IBU/polymer ratio. PMID:25749277

  9. Covalent Grafting of Tethered Homopolymer Film on p-Si(100).

    PubMed

    Zhang, Junhong; Li, Ming

    2016-04-19

    Covalent grafting of a homopolymer film onto a p-Si(100) surface was performed by use of surface electroinitiated emulsion polymerization. This polymerization method was one-step and cost-effective, and worked in the aqueous dispersed media containing both nitrobenzenediazonium (NBD) tetrafluoroborate and methyl methacrylate (MMA) monomer. NBD was reduced in the vicinity of substrate at the cut-on voltage of the pulsed voltage and was successively grafted on a Si surface, leading to a polynitrophenyl (PNP) layer. The reduction of NBD simultaneously initiated the polymerization of MMA. The resulting PMMA macroradicals in the solution can react with the previously grafted PNP at the cutoff voltage of the pulsed voltage for thickening the polymer film. The prepared polymer layer completely covered the Si surface, as investigated by the scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. Importantly, chemical components and the thickness of the grafted polymer film were well controlled by the applied voltage and the charge flow passing through the Si electrode. X-ray photoelectron spectroscopy (XPS) measurement further confirmed the Si-C bond between the polymer layer and the Si substrate. The homopolymer film was extremely effective in protecting the underlying Si from atmospheric oxidation. PMID:27022762

  10. Grafting glycidyl methacrylate to Sepharose gel for fabricating high-capacity protein anion exchangers.

    PubMed

    Wang, Qianqian; Yu, Linling; Sun, Yan

    2016-04-22

    To develop ion exchangers of high protein adsorption capacity, we have herein introduced atom transfer radical polymerization (ATRP) method to graft glycidyl methacrylate (GMA) onto Sepharose FF gel. GMA-grafted Sepharose FF resins of four grafting densities and different grafting chain lengths were obtained by adjusting reaction conditions. The epoxy groups on the grafted chains were functionalized by modification with diethylamine (DEA), leading to the fabrication of Sepharose-based anion exchangers of 14 different grafting densities and/or grafting chain lengths. The resins were first characterized for the effects of grafting density, chain length and ionic strength on pore sizes by inverse size exclusion chromatography. Then, the resins were evaluated by adsorption equilibria of bovine serum albumin (BSA) as a function of ionic capacity (IC) (chain length) at individual grafting densities. It was observed that at each grafting density there was a specific IC value (chain length) that offered the maximum equilibrium capacity. Of the resins with maximum values at individual grafting densities, the resin of the second grafting density with an IC value of 330 mmol/L (denoted as FF-Br2-pG-D330) showed the highest capacity, 264 mg/mL, about two times higher than that of the traditional ungrafted resin Q Sepharose FF (137 mg/mL). This resin also showed the most favorable uptake kinetics among the resins of similar IC values but different grafting densities, or of the same grafting density but different IC values. Effects of ionic strength showed that the capacities of FF-Br2-pG-D330 were much higher than Q Sepharose FF at a wide range of NaCl concentrations (0-200 mmol/L), and the uptake rates of the two resins were similar in the ionic strength range. Therefore, the dynamic binding capacity values of BSA on FF-Br2-pG-D330 were much higher than Q Sepharose FF as demonstrated at different residence times and ionic strengths. Taken together, the research has proved the

  11. Radiation

    NASA Video Gallery

    Outside the protective cocoon of Earth's atmosphere, the universe is full of harmful radiation. Astronauts who live and work in space are exposed not only to ultraviolet rays but also to space radi...

  12. Inhibition of protein adsorption and cell adhesion on PNIPAAm-grafted polyurethane surface: effect of graft molecular weight.

    PubMed

    Zhao, Tieliang; Chen, Hong; Zheng, Jun; Yu, Qian; Wu, Zhaoqiang; Yuan, Lin

    2011-06-15

    In this work, the effect of molecular weight (MW) of surface grafted poly(N-isopropylacrylamide) (PNIPAAm) on protein adsorption and cell adhesion was investigated systematically. PNIPAAm-grafted polyurethane (PU) surfaces of varying graft MW were prepared via conventional radical polymerization. The MW was controlled by adjusting the monomer concentration. Fibrinogen (Fg) and human serum albumin (HSA) were selected as model proteins and their adsorption from phosphate-buffered saline (PBS, pH 7.4) and blood plasma at 37°C was measured using a radiolabeling method and immunoblot analysis respectively. It was found that in both media, as the MW increased, the adsorption of these two proteins decreased gradually reaching a plateau value at MW above 7.9×10(4). Compared to the unmodified PU, the surface grafted with PNIPAAm of MW 14.6×10(4) reduced the adsorption of Fg and HSA in PBS by 91% and 86%, respectively. Moreover, the surfaces with higher MW PNIPAAm showed minimal adhesion of L929 cells presumably due to the absence of cell-adhesive proteins on the surfaces. PMID:21093225

  13. Antibacterial polypropylene via surface-initiated atom transfer radical polymerization.

    PubMed

    Huang, Jinyu; Murata, Hironobu; Koepsel, Richard R; Russell, Alan J; Matyjaszewski, Krzysztof

    2007-05-01

    Polypropylene (PP) coated by a non-leachable biocide was prepared by chemically attaching poly(quaternary ammonium) (PQA) to the surface of PP. The well-defined poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), a precursor of PQA, was grown from the surface of PP via atom transfer radical polymerization (ATRP). The tertiary ammine groups in PDMAEMA were consequently converted to QA in the presence of ethyl bromide. Successful surface modification was confirmed by ATR-FTIR, contact angle measurement, and an antibacterial activity test against Escherichia coli (E. coli). The biocidal activity of the resultant surfaces depends on the amount of the grafted polymers (the number of available quaternary ammonium units). With the same grafting density, the surface grafted with relatively high MW polymers (M(n) > 10,000 g/mol) showed almost 100% killing efficiency (killing all of the input E. coli (2.9 x 10(5)) in the shaking test), whereas a low biocidal activity (85%) was observed for the surface grafted with shorter PQA chains (M(n) = 1,500 g/mol). PMID:17417906

  14. Platelet adhesive resistance of segmented polyurethane film surface-grafted with vinyl benzyl sulfo monomer of ammonium zwitterions.

    PubMed

    Zhang, Jun; Yuan, Jiang; Yuan, Youling; Zang, Xiaopeng; Shen, Jian; Lin, Sicong

    2003-10-01

    Platelet from human plasma adhered on the segmented poly(ether urethane) (SPEU) film grafted with N,N-dimethyl-N-(p-vinylbenyl)-N-(3-sulfopropyl) ammonium (DMVSA) was studied. SPEU films were hydroxylated by potassium peroxosulfate (KPS) and then grafted with DMVSA using ceric ammonium nitrate (CAN) as initiator. The mixing time of hydroxylated SPEU/CAN and the monomer concentration effect on graft polymerization yield were determined by ATR-FTIR. Surface analysis of the grafted films by ATR-FTIR and ESCA confirmed that DMVSA was successfully grafted onto the SPEU film surface. The grafted film possessed a relatively hydrophilic surface, as revealed by water contact angle measurement. The improved blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion study and scanning electron microscopy, using original SPEU and hydroxylated SPEU films as the controls. The results showed that platelet attachment was decreased greatly on the segmented polyurethane films grafted with DMVSA. This kind of new biomaterials grafted with sulfo ammonium zwitterionic monomers might have potential for biomedical applications. PMID:12853253

  15. Grafting of GMA and some comonomers onto chitosan for controlled release of diclofenac sodium.

    PubMed

    Sharma, Rajeev Kr; Lalita; Singh, Anirudh P; Chauhan, Ghanshyam S

    2014-03-01

    In order to develop pH sensitive hydrogels for controlled drug release we have graft copolymerized glycidyl methacrylate (GMA) with comonomers acrylic acid, acrylamide and acrylonitrile, onto chitosan (Ch) by using potassium persulphate (KPS) as free radical initiator in aqueous solution. The optimum percent grafting for GMA was recorded for 1g chitosan at [KPS]=25.00 × 10(-3)mol/L, [GMA]=0.756 × 10(-3)mol/L, reaction temperature=60 °C and reaction time=1h in 20 mL H2O. Binary monomers were grafted for five different concentrations at optimum grafting conditions evaluated for GMA alone onto chitosan. The graft copolymers were characterized by FTIR, XRD, TGA and SEM. The swelling properties of chitosan and graft copolymers were investigated at different pH to define their end uses in sustained release of an anti-inflammatory drug, diclofenac sodium. Percent drug release w.r.t. drug loaded in polymeric sample was studied as function of time in buffer solutions of pH 2.0 and 7.4. In vitro release data was analyzed using Fick's Law. Chitosan grafted with binary monomers, GMA-co-AAm and GMA-co-AN showed very good results for sustained release of drug at 7.4 pH. PMID:24374084

  16. Oriented immobilization of proteins on grafted porous polymers

    NASA Astrophysics Data System (ADS)

    Carbajal, M. Laura; Smolko, Eduardo E.; Grasselli, Mariano

    2003-08-01

    The modification of polymers by radiation grafting has been utilized for several decades. The penetrability of gamma rays allows to modify the internal surfaces of porous materials retaining its mechanical properties. In recent years applications of these materials to obtain chromatographic supports and biocatalysts have been reported. In this work, we described the grafting of glycidyl methacrylate (GMA) onto a macroporous polysulfone polymer. Reproducible amount of grafting, from 10% to 60% was obtained by choosing favourable monomer concentration and gamma radiation doses from 6 kGy up. Afterwards, iminodiacetic acid (IDA) and amino phenyl arsine oxide (PAO) were covalently attached to the grafted polyGMA, in correspondence with the grafting degree. Later on, a recombinant histidin-patch thioredoxin protein (HP-rTrx) was immobilized onto this surface by two different ways, involving specific protein orientations. The first one involves an IDA-Ni 2+ complex and three HP-rTrx's histidines and the other one involves a co-ordination site between PAO and two proximal HP-rTrx's cysteines, which corresponds to the active site of the enzyme. Specific polyclonal antibodies recognize HP-rTrx on the polymer. Proper orientation of the protein was confirmed by HP-rTrx activity measurements. The described procedure allows the successful oriented immobilization of a protein onto a macroporous polysulfone material.

  17. Molecular architecture requirements for polymer-grafted lignin superplasticizers.

    PubMed

    Gupta, Chetali; Sverdlove, Madeline J; Washburn, Newell R

    2015-04-01

    Superplasticizers are a class of anionic polymer dispersants used to inhibit aggregation in hydraulic cement, lowering the yield stress of cement pastes to improve workability and reduce water requirements. The plant-derived biopolymer lignin is commonly used as a low-cost/low-performance plasticizer, but attempts to improve its effects on cement rheology through copolymerization with synthetic monomers have not led to significant improvements. Here we demonstrate that kraft lignin can form the basis for high-performance superplasticizers in hydraulic cement, but the molecular architecture must be based on a lignin core with a synthetic-polymer corona that can be produced via controlled radical polymerization. Using slump tests of ordinary Portland cement pastes, we show that polyacrylamide-grafted lignin prepared via reversible addition-fragmentation chain transfer polymerization can reduce the yield stress of cement paste to similar levels as a leading commercial polycarboxylate ether superplasticizer at concentrations ten-fold lower, although the lignin material produced via controlled radical polymerization does not appear to reduce the dynamic viscosity of cement paste as effectively as the polycarboxylate superplasticizer, despite having a similar affinity for the individual mineral components of ordinary Portland cement. In contrast, polyacrylamide copolymerized with a methacrylated kraft lignin via conventional free radical polymerization having a similar overall composition did not reduce the yield stress or the viscosity of cement pastes. While further work is required to elucidate the mechanism of this effect, these results indicate that controlling the architecture of polymer-grafted lignin can significantly enhance its performance as a superplasticizer for cement. PMID:25693832

  18. Grafting techniques for Peyronie's disease.

    PubMed

    Hatzichristodoulou, Georgios

    2016-06-01

    Peyronie's disease (PD) is a benign fibrotic condition of the penile tunica albuginea. PD can be associated with penile pain, curvature, shortening, and erectile dysfunction (ED). The predominant and most bothersome symptom in affected patients is penile curvature, which can lead to inability to have sexual intercourse. In such cases, surgical correction of the curvature may be required. Plication techniques to correct curvature can cause penile shortening and therefore are generally reserved for curvatures <60°. Penile prosthesis implantation with simultaneous correction of curvature by various means is recommended in PD patients with ED not responding to medical therapy. Grafting techniques are the preferred surgical treatment in patients with penile curvatures >60°, short penis, or hourglass deformity. Patients scheduled for grafting surgery are required to have satisfactory erectile rigidity preoperatively. There are various grafting materials that can be used for closure of the tunica albuginea defect following plaque incision/excision. Both autologous and non-autologous grafts have been used for PD reconstructive surgery, and each graft has its advantages and disadvantages. Novel grafting materials are presented and discussed in this review. A major advantage of the available "off-the-shelf" grafts is that there is no harvesting from a donor site and, thus, morbidity is reduced, and operative times are minimized. Further investigations in regard to tissue-engineered grafts to improve surgical handling and postoperative outcomes are ongoing. Surgeon experience, careful patient selection, patient preference and type of penile deformity affect the choice of graft. This review summarizes the literature within the past 5 years regarding grafting techniques in PD. Surgical outcomes and limitations of grafting techniques are reported. A major objective of this review is dedicated to preoperative considerations and indications for grafting procedures, with the aim

  19. Applications of skin grafting in large animals.

    PubMed

    Wilson, D G

    1990-09-01

    Injuries involving full-thickness skin wounds are common in large animals. Skin grafting can shorten the healing time and improve the cosmetic result. Techniques that have been used successfully in the management of full-thickness skin wounds include full-thickness skin grafts, split-thickness skin grafts, tunnel grafts, pinch/punch grafts, and immediate split-thickness skin grafts. The technical aspects of each of these procedures are detailed and representative cases are presented. PMID:2134606

  20. Preparation of an Antibacterial Poly(ionic liquid) Graft Copolymer of Hydroxyethyl Cellulose.

    PubMed

    Joubert, Fanny; Yeo, R Paul; Sharples, Gary J; Musa, Osama M; Hodgson, David R W; Cameron, Neil R

    2015-12-14

    Poly(ionic liquid)s (P(IL)s) of different degrees of polymerization (10, 50, and 100) were prepared via RAFT polymerization using an alkyne-terminated xanthate as transfer agent, with a monomer conversion of up to ∼80% and a ĐM of 1.5 for P(IL)100. Subsequently, P(IL) chains were coupled to (15)N-labeled azido-functionalized hydroxyethyl cellulose (HEC), forming graft copolymers of HEC with different chain length and graft densities, which were characterized using ((13)C and (15)N) CP-MAS NMR and FT-IR spectroscopies. The antibacterial activities of HEC-g-P(IL)s were tested against Escherichia coli and Staphylococcus aureus and were comparable to ampicillin, a well-known antibiotic, demonstrating efficient activity of the graft copolymers against bacteria. Moreover, HEC-g-P(IL)s were slightly more effective against E. coli than S. aureus. A decrease in graft density of P(IL)10 on the HEC backbone decreased the activity of the graft copolymers against both bacteria. These findings suggest that HEC-g-P(IL) could find applications as an antiseptic compound, for example, in paint formulation. PMID:26544047

  1. Enzymatic Hydrophobic Modification of Jute Fibers via Grafting to Reinforce Composites.

    PubMed

    Liu, Ruirui; Dong, Aixue; Fan, Xuerong; Yu, Yuanyuan; Yuan, Jiugang; Wang, Ping; Wang, Qiang; Cavaco-Paulo, Artur

    2016-04-01

    Horseradish peroxidase (HRP)/H2O2 system catalyzes the free-radical polymerization of aromatic compounds such as lignins and gallate esters. In this work, dodecyl gallate (DG) was grafted onto the surfaces of lignin-rich jute fabrics by HRP-mediated oxidative polymerization with an aim to enhance the hydrophobicity of the fibers. The DG-grafted jute fibers and reaction products of their model compounds were characterized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results clearly indicated the grafting of DG to the jute fiber by HRP. Furthermore, the hydrophobicity of jute fabrics was determined by measuring the wetting time and static contact angle. Compared to the control sample, the wetting time and static contact angle of the grated fabrics changed from ~1 s to 1 h and from ~0° to 123.68°, respectively. This clearly proved that the hydrophobicity of jute fabrics improved considerably. Conditions of the HRP-catalyzed DG-grafting reactions were optimized in terms of the DG content of modified jute fabrics. Moreover, the results of breaking strength and elongation of DG-grafted jute/polypropylene (PP) composites demonstrated improved reinforcement of the composite due to enzymatic hydrophobic modification of jute fibers. PMID:26754422

  2. Polymeric blends for sensor and actuation dual functionality

    NASA Technical Reports Server (NTRS)

    St. Clair, Terry L. (Inventor); Harrison, Joycelyn S. (Inventor); Su, Ji (Inventor); Ounaies, Zoubeida (Inventor)

    2004-01-01

    The invention described herein supplies a new class of electroactive polymeric blend materials which offer both sensing and actuation dual functionality. The blend comprises two components, one component having a sensing capability and the other component having an actuating capability. These components should be co-processable and coexisting in a phase separated blend system. Specifically, the materials are blends of a sensing component selected from the group consisting of ferroelectric, piezoelectric, pyroelectric and photoelectric polymers and an actuating component that responds to an electric field in terms of dimensional change. Said actuating component includes, but is not limited to, electrostrictive graft elastomers, dielectric electroactive elastomers, liquid crystal electroactive elastomers and field responsive polymeric gels. The sensor functionality and actuation functionality are designed by tailoring the relative fraction of the two components. The temperature dependence of the piezoelectric response and the mechanical toughness of the dual functional blends are also tailored by the composition adjustment.

  3. Frontal Polymerization in Microgravity

    NASA Technical Reports Server (NTRS)

    Pojman, John A.

    1999-01-01

    Frontal polymerization systems, with their inherent large thermal and compositional gradients, are greatly affected by buoyancy-driven convection. Sounding rocket experiments allowed the preparation of benchmark materials and demonstrated that methods to suppress the Rayleigh-Taylor instability in ground-based research did not significantly affect the molecular weight of the polymer. Experiments under weightlessness show clearly that bubbles produced during the reaction interact very differently than under 1 g.

  4. Polymeric Bicontinuous Microemulsions

    NASA Astrophysics Data System (ADS)

    Bates, Frank S.; Maurer, Wayne W.; Lipic, Paul M.; Hillmyer, Marc A.; Almdal, Kristoffer; Mortensen, Kell; Fredrickson, Glenn H.; Lodge, Timothy P.

    1997-08-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in mixtures containing a model diblock copolymer and two homopolymers. Although we attribute development of this equilibrium morphology to the effects of fluctuations, mean-field theory provides a quantitative strategy for preparing the bicontinuous state at blend compositions near an isotropic Lifshitz point.

  5. Surface polymerization agents

    SciTech Connect

    Taylor, C.; Wilkerson, C.

    1996-12-01

    This is the final report of a 1-year, Laboratory-Directed R&D project at LANL. A joint technical demonstration was proposed between US Army Missile Command (Redstone Arsenal) and LANL. Objective was to demonstrate that an unmanned vehicle or missile could be used as a platform to deliver a surface polymerization agent in such a manner as to obstruct the filters of an air-breathing mechanism, resulting in operational failure.

  6. Suspended polymeric photonic crystals: simulation and fabrication

    NASA Astrophysics Data System (ADS)

    Rebigan, R.; Dinescu, A.; Kusko, C.; Gavrila, R.; Cristea, D.; Obreja, C.; Schiopu, P.

    2010-11-01

    In this paper we present simulation of transmission / reflection spectra of polymeric rectangular and hexagonal photonic crystals (PC) as well as the propagation of radiation in a hexagonal PC - based waveguide. The polymeric PC are periodic structures consisting in square arrays of holes configured in suspended membranes of PMMA with different diameters and pitch (100 nm diameter with 500 nm, respectively 800 nm pitch; 200 nm diameter with 500 nm pitch; 400 nm diameter with 700 nm pitch). For fabrication, we propose the bi-layer EBL technique based on simultaneous patterning of a bottom sacrificial layer (LOR 5A - Microchem Corporation) and a positive electron resist (PMMA of different molecular weights). Characterization of nanostructures was performed using SEM imaging and AFM measurements .

  7. Durability of Polymeric Glazing and Absorber Materials

    SciTech Connect

    Jorgensen, G.; Terwilliger, K.; Bingham, C.; Milbourne, M.

    2005-01-01

    The Solar Heating and Lighting Program has set the goal of reducing the cost of solar water heating systems by at least 50%. An attractive approach to such large cost reduction is to replace glass and metal parts with less-expensive, lighter-weight, more-integrated polymeric components. The key challenge with polymers is to maintain performance and assure requisite durability for extended lifetimes. The objective of this task is to quantify lifetimes through measurement of the optical and mechanical stability of candidate polymeric glazing and absorber materials. Polycarbonate sheet glazings, as proposed by two industry partners, have been tested for resistance to UV radiation with three complementary methods. Incorporation of a specific 2-mil thick UV-absorbing screening layer results in glazing lifetimes of at least 15 years; improved screens promise even longer lifetimes. Proposed absorber materials were tested for creep and embrittlement under high temperature, and appear adequate for planned ICS absorbers.

  8. RAFT-synthesized Graft Copolymers that Enhance pH-dependent Membrane Destabilization and Protein Circulation Times

    PubMed Central

    Crownover, Emily; Duvall, Craig L.; Convertine, Anthony; Hoffman, Allan S.; Stayton, Patrick S.

    2012-01-01

    Here we describe a new graft copolymer architecture of poly(propylacrylic acid) (polyPAA) that displays potent pH-dependent, membrane-destabilizing activity and in addition is shown to enhance protein blood circulation kinetics. PolyPAA containing a single telechelic alkyne functionality was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization with an alkyne-functional chain transfer agent (CTA) and coupled to RAFT polymerized poly(azidopropyl methacrylate) (polyAPMA) through azide-alkyne [3+2] Huisgen cycloaddition. The graft copolymers become membrane destabilizing at endosomal pH values and are active at significantly lower concentrations than the linear polyPAA. A biotin terminated polyPAA graft copolymer was prepared by grafting PAA onto polyAPMA polymerized with a biotin functional RAFT CTA. The blood circulation time and biodistribution of tritium labeled avidin conjugated to the polyPAA graft copolymer was characterized along with a clinically utilized 40 kDa branched polyethylene glycol (PEG) also possessing biotin functionalization. The linear and graft polyPAA increase the area under the curve (AUC) over avidin alone by 9 and 12 times, respectively. Furthermore, polyPAA graft copolymer conjugates accumulated in tumor tissue significantly more than the linear polyPAA and the branched PEG conjugates. The collective data presented in this report indicate that the polyPAA graft copolymers exhibit robust pH-dependent, membrane-destabilizing activity, low cytotoxicity and significantly enhance blood circulation time and tumor accumulation. PMID:21699931

  9. Polyether/Polyester Graft Copolymers

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

    1986-01-01

    Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

  10. Gluteus augmentation with fat grafting.

    PubMed

    Perén, P A; Gómez, J B; Guerrerosantos, J; Salazar, C A

    2000-01-01

    This study presents the authors' experience with gluteus augmentation with autologus fat grafts and liposuction methods, having recorded the evolution of gluteus reshaping with autologus intramuscular fat graft injections for the past 5 years. Preoperative shape is discussed and patient evaluations, operative techniques, postoperative management, and longterm results are emphasized. PMID:11246428

  11. Grafting effects on vegetable quality

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable grafting began in the 1920s to control soil-borne disease. It is now a common practice in Asia, parts of Europe, and the Middle East. In Japan and Korea most of the cucurbits and tomatoes (Lycopersicon esculentum Mill.) grown are grafted. This practice is rare in the U.S. and there have...

  12. Listeria monocytogenes Endovascular Graft Infection

    PubMed Central

    Heysell, Scott K.; Hughes, Molly A.

    2016-01-01

    Although best managed by surgical resection, we present a case of Listeria monocytogenes endovascular graft infection alternatively treated with graft retention and antibiotic induction followed by a lifelong suppressive course. The epidemiological, pathological, and clinical features of this unique entity are reviewed. PMID:26835477

  13. Nanostructured and Surface Polymerized Iron Particles for Magnetorheological Fluids

    NASA Astrophysics Data System (ADS)

    Hu, Ben; Fuchs, Alan; Gordaninejad, Faramarz; Evrensel, Cahit

    A novel magnetorheological fluid, in which the surface of iron particles is coated with poly (butyl acrylate) by surface initiated atom transfer radical polymerization (ATRP), is investigated. The polymer coating procedure includes two steps, which are immobilization of initiator: 2-4(-chlorosulfonylphenyl)-ethytrichlorosilane (CTCS) on the iron particles surface and graft polymerization of butyl acrylate from the surface. The surface coating is characterized by FTIR and SEM. This magnetorheological fluid has controllable off-state viscosity and high shear yield stress. Coating polymer on the iron particles surface by ATRP can significantly reduce iron particles settling and improve stability of the MR fluid. Polymerization kinetics of bulk butyl acrylate are investigated using differential scanning calorimetry (DSC). Glass transition temperature is obtained using the step-scan DSC method. The molecular weight and conversion can be controlled by the molar ratio of monomer to initiator, reaction temperature and time. The reaction is first order determined by the plot of In (M/M0) against polymerization time. The overall activation energy is found to be 126kJ/mol by Kissinger's Method.

  14. Properties of amylose-oleic acid inclusion complexes from corn starch grafted with poly(methyl acrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Corn starch granules have been previously investigated as fillers in polymers. In this study, much smaller particles in the form of spherulites produced by steam jet-cooking high-amylose corn starch and oleic acid to form amylose inclusion complexes were graft polymerized with methyl acrylate, both ...

  15. [Stent Grafting for Aortic Dissection].

    PubMed

    Uchida, Naomichi

    2016-07-01

    The purpose of stent graft for aortic dissection is to terminate antegrade blood flow into the false lumen through primary entry. Early intervention for primary entry makes excellent aortic remodeling and emergent stent grafting for complicated acute type B aortic dissection is supported as a class I. On the other hand stent grafting for chronic aortic dissection is controversial. Early stent grafting is considered with in 6 months after on-set if the diameter of the descending aorta is more than 40 mm. Additional interventions for residual false lumen on the downstream aorta are still required. Stent graft for re-entry, candy-plug technique, and double stenting, other effective re-interventions were reported. Best treatment on the basis of each anatomical and physical characteristics should be selected in each institution. Frozen elephant trunk is alternative procedure for aortic dissection without the need to take account of proximal anatomical limitation and effective for acute type A aortic dissection. PMID:27440026

  16. ACL Reconstruction: Choosing the Graft

    PubMed Central

    Cerulli, Giuliano; Placella, Giacomo; Sebastiani, Enrico; Tei, Matteo Maria; Speziali, Andrea; Manfreda, Francesco

    2013-01-01

    Summary Rupture of the anterior cruciate ligament is one of the most common ligament injuries in sports traumatology. The need for surgical anterior cruciate ligament reconstruction is justified by its anatomical characteristics. Key considerations when choosing a graft include the potential for bone integration and the risk of failure. Bone sclerosis around the tunnel affects the integration of the graft. For this reason, one aspect upon which orthopedic surgeons should focus is the biology of the bone-graft interface. Although the BPTB graft is still used, hamstrings and synthetic grafts have become increasingly widespread and popular over the years. An allograft certainly requires more long-term follow-up to validate its use in response to functional, clinical and biological requirements. PMID:25606507

  17. An ultra-sensitive microfluidic immunoassay using living radical polymerization and porous polymer monoliths.

    SciTech Connect

    Abhyankar, Vinay V.; Singh, Anup K.; Hatch, Anson V.

    2010-07-01

    We present a platform that combines patterned photopolymerized polymer monoliths with living radical polymerization (LRP) to develop a low cost microfluidic based immunoassay capable of sensitive (low to sub pM) and rapid (<30 minute) detection of protein in 100 {micro}L sample. The introduction of LRP functionality to the porous monolith allows one step grafting of functionalized affinity probes from the monolith surface while the composition of the hydrophilic graft chain reduces non-specific interactions and helps to significantly improve the limit of detection.

  18. Physicochemical Properties of 'Particle Brush'-Based Materials: Using Polymer Graft Modification to Tailor Particle Interactions

    NASA Astrophysics Data System (ADS)

    Schmitt, Michael D.

    The advent of surface-initiated controlled radical polymerization techniques has allowed a new class of hybrid polymer-grafted nanoparticles, known as eparticle brushes,f to be realized. By grafting polymers from the surface, interactions between particles can be tuned using the precise control over graft architecture (i.e. chain length, dispersity, particle size, and grafting density) afforded by controlled radical polymerizations. Previously, a transition from particle-like to polymer-like interactions in small particles with increasing graft length has been observed. In the limit of long graft lengths, the polymer chains impart new interactions between particles, such as entanglements. These results outline a rich, but largely unexplored parameter space. The present thesis further elucidates the extent to which polymer graft modification facilitates new interaction types between particles and the dependence of those interactions on chain conformation. Specifically, the mechanical properties, processability, phase separation, and vibrational modes of particle brushes are examined. A dependence of the mechanical properties of particle brush assemblies on particle size is accurately captured by accounting for differences in chain conformation between particles of different sizes using a simple scaling model. Further tailoring of mechanical characteristics in weak particle brush assemblies can be achieved using appropriate homopolymer additives to form two-component systems. Improved mechanical properties are accompanied by a significant enhancement in particle processability that allows application of previously unusable processing methods. Considering more complex systems, mesoscale phase separation of nanoparticles is demonstrated for the first time by blending of particle brushes with different graft polymers. Polymer graft modification is seen to not only strengthen and introduce new interactions, but also tune particle properties. Vibrational modes of

  19. Synthesis of graft copolymers based on poly(2-methoxyethyl acrylate) and investigation of the associated water structure.

    PubMed

    Javakhishvili, Irakli; Tanaka, Masaru; Ogura, Keiko; Jankova, Katja; Hvilsted, Søren

    2012-02-27

    Graft copolymers composed of poly(2-methoxyethyl acrylate) are prepared employing controlled radical polymerization techniques. Linear backbones bearing atom transfer radical polymerization (ATRP) initiating sites are obtained by reversible addition-fragmentation chain transfer copolymerization of 2-methoxyethyl acrylate (MEA) and 2-(bromoisobutyryloxy)ethyl methacrylate (Br(i) BuEMA) as well as 2-hydroxyethyl methacrylate and Br(i) BuEMA in a controlled manner . MEA is then grafted from the linear macroinitiators by Cu (I)-mediated ATRP. Fairly high molecular weights (>120 000 Da) and low polydispersity indices (1.17-1.38) are attained. Thermal investigations of the graft copolymers indicate the presence of the freezing bound water, and imply that the materials may exhibit blood compatibility. PMID:22271568

  20. Synthesis of perm-selective membranes by grafting acrylic acid into air-irradiated Teflon-FEP films

    NASA Astrophysics Data System (ADS)

    Bozzi, Annick; Chapiro, Adolphe

    Grafting acrylic acid into air-irradiated Teflon-FEP films was investigated. Pre-irradiation doses ranged from 0.5 to 10 kGy. Grafting occurred at 45 or 60°C. Homopolymerization inhibitors, ferrous ions or methylene blue, were added to the system. It was found that after completion of the reaction, within 40-100 min, membranes were obtained with very low electric resistivities. The influence of added inhibitors, pre-irradiation dose and grafting temperature was studied. From the results it is concluded that the initiating centers in air-irradiated Teflon-FEP are, on the one hand, peroxides of structure POOP', in which P is a polymeric radical and Pprime; a small fragment, and on the other trapped PO .2 radicals. The latter only react after losing their oxygen. In the presence of polymerization inhibitors, initiation involves a redox process which reduces the overall activation energy.

  1. Self-assembly of well-defined polyacrylamide-polystyrene copolymer on fibrillar clays via ultrasonic-assisted surface-initiated atom transfer radical polymerization.

    PubMed

    Liu, Peng; Wang, Tingmei; Su, Zhixing

    2006-06-01

    Well-defined polyacrylamide-polystyrene copolymers were grafted from the fibrillar clay, attapulgite, by a four-step self-assembly process: (i) the gamma-aminopropyltriethoxyl silane was self-assembled onto the surfaces of the attapulgite; (ii) the surface amino groups were amidated with bromoacetylbromide; (iii) the bromo-acetamide modified attapulgite was used as macro-initiator for the surface-initiated atom transfer radical polymerization of styrene with the catalyst of the complex of 1,10-phenanthroline and Cu(I)Br; (iv) the polystyrene grafted attapulgite was then used as macroinitiator for the polymerization of acrylamide. The two steps of the surface-initiated atom transfer radical polymerizations were all conducted under ultrasonic irradiation at room temperature. The product, polyacrylamide-polystyrene copolymers grafted attapulgite, had been characterized with elemental analysis, Fourier transform infrared spectroscopy, Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy. PMID:17025071

  2. The grafting of a thin layer of poly(sodium styrene sulfonate) onto poly(ε-caprolactone) surface can enhance fibroblast behavior

    PubMed Central

    Rohman, Géraldine; Huot, Stéphane; Vilas-Boas, Maria; Radu-Bostan, Gabriela; Castner, David G.; Migonney, Véronique

    2015-01-01

    Poly(sodium styrene sulfonate) (pNaSS) was grafted onto poly(ε-caprolatone) (PCL) surfaces via ozonation and graft polymerization. The effect of ozonation and polymerization time, as well as the Mohr’s salt concentration in the grafting solution, on the degree of grafting was investigated. The degree of grafting was determined through toluidine blue staining. The surface chemical change was characterized by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The result demonstrated that the grafting did not induce any degradation of PCL, and that pNaSS was grafted onto PCL as a thin and covalently stable layer. Furthermore, the modified PCL surface reveals a significant increase in the metabolic activity of fibroblastic cells, as well as a better cell spreading with higher adhesion strength. Consequently, bioactivity of PCL is greatly enhanced by immobilizing a thin layer of pNaSS onto its surface. The grafting of pNaSS is a promising approach to increase the bioactivity of PCL-based materials used in tissue engineering applications, such as ligament reconstruction. PMID:26155977

  3. The grafting of a thin layer of poly(sodium styrene sulfonate) onto poly(ε-caprolactone) surface can enhance fibroblast behavior.

    PubMed

    Rohman, Géraldine; Huot, Stéphane; Vilas-Boas, Maria; Radu-Bostan, Gabriela; Castner, David G; Migonney, Véronique

    2015-07-01

    Poly(sodium styrene sulfonate) (pNaSS) was grafted onto poly(ε-caprolatone) (PCL) surfaces via ozonation and graft polymerization. The effect of ozonation and polymerization time, as well as the Mohr's salt concentration in the grafting solution, on the degree of grafting was investigated. The degree of grafting was determined through toluidine blue staining. The surface chemical change was characterized by attenuated total reflection Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The result demonstrated that the grafting did not induce any degradation of PCL, and that pNaSS was grafted onto PCL as a thin and covalently stable layer. Furthermore, the modified PCL surface reveals a significant increase in the metabolic activity of fibroblastic cells, as well as a better cell spreading with higher adhesion strength. Consequently, bioactivity of PCL is greatly enhanced by immobilizing a thin layer of pNaSS onto its surface. The grafting of pNaSS is a promising approach to increase the bioactivity of PCL-based materials used in tissue engineering applications, such as ligament reconstruction. PMID:26155977

  4. Polymeric salt bridges for conducting electric current in microfluidic devices

    DOEpatents

    Shepodd, Timothy J.; Tichenor, Mark S.; Artau, Alexander

    2009-11-17

    A "cast-in-place" monolithic microporous polymer salt bridge for conducting electrical current in microfluidic devices, and methods for manufacture thereof is disclosed. Polymeric salt bridges are formed in place in capillaries or microchannels. Formulations are prepared with monomer, suitable cross-linkers, solvent, and a thermal or radiation responsive initiator. The formulation is placed in a desired location and then suitable radiation such as UV light is used to polymerize the salt bridge within a desired structural location. Embodiments are provided wherein the polymeric salt bridges have sufficient porosity to allow ionic migration without bulk flow of solvents therethrough. The salt bridges form barriers that seal against fluid pressures in excess of 5000 pounds per square inch. The salt bridges can be formulated for carriage of suitable amperage at a desired voltage, and thus microfluidic devices using such salt bridges can be specifically constructed to meet selected analytical requirements.

  5. Polymerization Evaluation by Spectrophotometric Measurements.

    ERIC Educational Resources Information Center

    Dunach, Jaume

    1985-01-01

    Discusses polymerization evaluation by spectrophotometric measurements by considering: (1) association degrees and molar absorptivities; (2) association degrees and equilibrium constants; and (3) absorbance and equilibrium constants. (JN)

  6. Sustainable polymerizations in recoverable microemulsions.

    PubMed

    Chen, Zhenzhen; Yan, Feng; Qiu, Lihua; Lu, Jianmei; Zhou, Yinxia; Chen, Jiaxin; Tang, Yishan; Texter, John

    2010-03-16

    Free radical and atom-transfer radical polymerizations were conducted in monomer/ionic liquid microemulsions. After the polymerization and isolation of the resultant polymers, the mixture of the catalyst and ionic liquids (surfactant and continuous phase) can be recovered and reused, thereby dramatically improving the environmental sustainability of such chemical processing. The addition of monomer to recovered ionic liquid mixtures regenerates transparent, stable microemulsions that are ready for the next polymerization cycle upon addition of initiator. The method combines the advantages of IL recycling and microemulsion polymerization and minimizes environmental disposable effects from surfactants and heavy metal ions. PMID:20170175

  7. Robot-assisted antegrade in-situ fenestrated stent grafting.

    PubMed

    Riga, Celia V; Bicknell, Colin D; Wallace, Daniel; Hamady, Mohamad; Cheshire, Nicholas

    2009-05-01

    To determine the technical feasibility of a novel approach of in-situ fenestration of aortic stent grafts by using a remotely controlled robotic steerable catheter system in the porcine model. A 65-kg pig underwent robot-assisted bilateral antegrade in-situ renal fenestration of an abdominal aortic stent graft with subsequent successful deployment of a bare metal stent into the right renal artery. A 16-mm iliac extension covered stent served as the porcine aortic endograft. Under fluoroscopic guidance, the graft was punctured with a 20-G customized diathermy needle that was introduced and kept in place by the robotic arm. The needle was exchanged for a 4 x 20 mm cutting balloon before successful deployment of the renal stent. Robot-assisted antegrade in-situ fenestration is technically feasible in a large mammalian model. The robotic system enables precise manipulation, stable positioning, and minimum instrumentation of the aorta and its branches while minimizing radiation exposure. PMID:18972158

  8. Immobilization of bacteria in microgel grafted onto macroporous polyethylene

    NASA Astrophysics Data System (ADS)

    Trelles, J. A.; Quiroga, F.; Britos, C.; Smolko, Eduardo E.; Grasselli, Mariano

    2010-03-01

    The development of " Green Chemistry" requires new materials to replace the conventional organic chemistry by biological catalysts, to produce fine chemicals in an environmentally friendly manner. Microbial whole cells can be directly used as biocatalysts, providing a simple and cheap methodology since enzyme isolation and purification are avoided. High-density polyethylene (HDPE) is a very stable polymer though it can be activated by gamma radiation to induce grafting. Glycidyl methacrylate was grafted onto macroporous HDPE and PP in the range of 1-6%, proportional to the initial monomer concentration. Grafted polymers were further chemically modified with ethylenediamine to generate a cationic hydrogel of micron-size thickness onto the internal polymer surfaces. Modified polymers were able to immobilize Gram-positive and Gram-negative bacteria that can catalyze a chemical reaction as efficient as free cells do.

  9. Robot-Assisted Antegrade In-Situ Fenestrated Stent Grafting

    SciTech Connect

    Riga, Celia V. Bicknell, Colin D.; Wallace, Daniel; Hamady, Mohamad; Cheshire, Nicholas

    2009-05-15

    To determine the technical feasibility of a novel approach of in-situ fenestration of aortic stent grafts by using a remotely controlled robotic steerable catheter system in the porcine model. A 65-kg pig underwent robot-assisted bilateral antegrade in-situ renal fenestration of an abdominal aortic stent graft with subsequent successful deployment of a bare metal stent into the right renal artery. A 16-mm iliac extension covered stent served as the porcine aortic endograft. Under fluoroscopic guidance, the graft was punctured with a 20-G customized diathermy needle that was introduced and kept in place by the robotic arm. The needle was exchanged for a 4 x 20 mm cutting balloon before successful deployment of the renal stent. Robot-assisted antegrade in-situ fenestration is technically feasible in a large mammalian model. The robotic system enables precise manipulation, stable positioning, and minimum instrumentation of the aorta and its branches while minimizing radiation exposure.

  10. Continuous polymerization reactor

    SciTech Connect

    Wilt, M.S.

    1986-05-06

    A method is described for contacting olefinic monomer and initiator in a continuous polymerization process comprising of the steps of: creating three turbulent zones in a vessel; introducing the olefinic monomer into a first part of the periphery of each one of the three turbulent zones; introducing the initiator into a second part of the periphery of each one of the three turbulent zones, wherein the first part of the periphery of each one of the three turbulent zones is substantially diametrically opposed to the second part of the periphery of each one of the three turbulent zones respectively.

  11. Bimorphic polymeric photomechanical actuator

    NASA Technical Reports Server (NTRS)

    Sarkisov, Sergey S. (Inventor); Curley, Michael J. (Inventor); Adamovsky, Grigory (Inventor); Sarkisov, Jr., Sergey S. (Inventor); Fields, Aisha B. (Inventor)

    2006-01-01

    A bimorphic polymeric photomechanical actuator, in one embodiment using polyvinylidene fluoride (PVDF) as a photosensitive body, transmitting light over fiber optic cables, and controlling the shape and pulse duration of the light pulse to control movement of the actuator. Multiple light beams are utilized to generate different ranges of motion for the actuator from a single photomechanical body and alternative designs use multiple light beams and multiple photomechanical bodies to provide controlled movement. Actuator movement using one or more ranges of motion is utilized to control motion to position an actuating element in three dimensional space.

  12. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Bauman, Robert

    2006-11-14

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  13. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    2003-08-26

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  14. Living olefin polymerization processes

    DOEpatents

    Schrock, R.R.; Baumann, R.

    1999-03-30

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  15. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  16. Polymer grafted hydroxyapatite whisker as a filler for dental composite resin with enhanced physical and mechanical properties.

    PubMed

    Liu, Fengwei; Wang, Ruili; Cheng, Yanhua; Jiang, Xiaoze; Zhang, Qinghong; Zhu, Meifang

    2013-12-01

    The objective of this study was to investigate the effect of surface graft polymerization of hydroxyapatite whisker (HW) on physical and mechanical properties of dental composite resin. Poly bisphenol A glycidyl methacrylate (Poly(Bis-GMA)) was grafted onto silanized hydroxyapatite whisker (SHW) via solution polymerization and the amount of the Poly(Bis-GMA) on the surface was effectively controlled by polymerization time. The obtained poly(Bis-GMA) grafted hydroxyapatite whisker (PGHW) with different polymer contents was filled into a resin matrix respectively, meanwhile the composites with HW and with SHW served as controls. Monomer conversion was characterized by Fourier transform infrared spectroscopy (FTIR) and volume shrinkage of the composite resin was measured with a density tester. Mechanical properties were tested with a universal testing machine. The results indicated that the composite filled with PGHW-1h (graft ratio of poly(Bis-GMA): 8.5 wt.%) showed lower shrinkage and better mechanical properties, improving flexural strength by 6.5% and 11.9% compared with SHW filled composite and HW filled composite, respectively. However, PGHW with higher graft ratios aggregated seriously and formed defects in the composite, leading to deterioration of mechanical properties. It was revealed that the poly(Bis-GMA) on the surface of PGHW acted as a functional transition layer and enhanced interfacial compatibility and interaction between whisker and resin matrix, which facilitated the dispersion of PGHW in the composite and decreased the composite shrinkage. Thus, the graft polymerization of Bis-GMA on the surface of filler might be a promising modification method for the fabrication of dental materials. PMID:24094216

  17. Hemocompatible control of sulfobetaine-grafted polypropylene fibrous membranes in human whole blood via plasma-induced surface zwitterionization.

    PubMed

    Chen, Sheng-Han; Chang, Yung; Lee, Kueir-Rarn; Wei, Ta-Chin; Higuchi, Akon; Ho, Feng-Ming; Tsou, Chia-Chun; Ho, Hsin-Tsung; Lai, Juin-Yih

    2012-12-21

    In this work, the hemocompatibility of zwitterionic polypropylene (PP) fibrous membranes with varying grafting coverage of poly(sulfobetaine methacrylate) (PSBMA) via plasma-induced surface polymerization was studied. Charge neutrality of PSBMA-grafted layers on PP membrane surfaces was controlled by the low-pressure and atmospheric plasma treatment in this study. The effects of grafting composition, surface hydrophilicity, and hydration capability on blood compatibility of the membranes were determined. Protein adsorption onto the different PSBMA-grafted PP membranes from human fibrinogen solutions was measured by enzyme-linked immunosorbent assay (ELISA) with monoclonal antibodies. Blood platelet adhesion and plasma clotting time measurements from a recalcified platelet-rich plasma solution were used to determine if platelet activation depends on the charge bias of the grafted PSBMA layer. The charge bias of PSBMA layer deviated from the electrical balance of positively and negatively charged moieties can be well-controlled via atmospheric plasma-induced interfacial zwitterionization and was further tested with human whole blood. The optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and keeps its original blood-inert property of antifouling, anticoagulant, and antithrmbogenic activities when it comes into contact with human blood. This work suggests that the hemocompatible nature of grafted PSBMA polymers by controlling grafting quality via atmospheric plasma treatment gives a great potential in the surface zwitterionization of hydrophobic membranes for use in human whole blood. PMID:23181727

  18. Novel Synthesis of Surface-Grafted Radical Initiator With Improved Stability and Yield

    NASA Astrophysics Data System (ADS)

    Bain, Erich; Dawes, Keith; Hu, Xinfang; Gorman, Christopher; Srogl, Jiri; Genzer, Jan

    2012-02-01

    Polymers grafted at interfaces are attractive for applications including antifouling coatings, biologically functionalized materials, and responsive surfaces. The ``grafting from'' approach to form densely packed brushes involves functionalizing a substrate with initiating moieties, and carrying out polymerization, e.g., surface-inititated free-radical polymerization (SI-FRP). Azo initiators for SI-FRP are commonly synthesized by a low-yielding route requiring large amounts of potassium cyanide. Those initiators are linked to a substrate by means of an ester group, rendering tethered polymers susceptible to degrafting by hydrolysis. We present a novel synthetic route to an asymmetric azo initiator, whose yield is nearly double that of previous syntheses. Cyanide usage in the new method is reduced by 72 percent. The spacer linking the initiator to a substrate contains only carbon-carbon bonds, resulting in stable brushes. Results are demonstrated for SI-FRP as well as reverse ATRP and RAFT.

  19. Secondary alveolar bone grafting: our experience with olecranon bone graft.

    PubMed

    Nadal, Emmanuela; Sabás, Mariana; Dogliotti, Pedro; Espósito, Raquel

    2010-03-01

    Management of alveolar cleft has dramatically changed during the last century: secondary alveolar bone grafting is now an integral part of cleft palate and craniofacial center's protocols. The objectives of alveolar repair and bone grafting are as follows: providing a continuous and stable maxillary dental arch, closure of oronasal fistulae, adequate bone for tooth eruption or orthodontic movement, and nasal base support, improving facial aesthetic. Although cancellous iliac bone is the donor site selected more frequently, bone grafts harvested from different sites have been advocated to decrease donor site morbidity.The aim of this study was to propose and evaluate the use of olecranon as a donor site in 24 patients with secondary alveolar cleft. The graft is taken as a single piece to fit the alveolar cleft defect, and it includes periosteum and corticocancellous bone to improve early vascularization and greater volume maintenance. PMID:20186086

  20. Space environmental effects on polymeric materials

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.; Orwoll, Robert A.

    1988-01-01

    Polymer-matrix composites have considerable potential for use in the construction of orbiting structures such as the space station and space antennas because of their light weight, high strength, and low thermal expansion. However, they can suffer surface erosion by interaction with atomic oxygen in low-Earth orbit and degradation and/or embrittlement by electrons and ultraviolet radiation especially in geosynchronous orbit. Thus, a study of the effect of these environmental hazards on polymeric materials is an important step in the assessment of such materials for future use in space.

  1. Fat Grafting for Facial Filling and Regeneration.

    PubMed

    Coleman, Sydney R; Katzel, Evan B

    2015-07-01

    Plastic surgeons have come to realize that fat grafting can rejuvenate an aging face by restoring or creating fullness. However, fat grafting does much more than simply add volume. Grafted fat can transform or repair the tissues into which it is placed. Historically, surgeons have hesitated to embrace the rejuvenating potential of fat grafting because of poor graft take, fat necrosis, and inconsistent outcomes. This article describes fat grafting techniques and practices to assist readers in successful harvesting, processing, and placement of fat for optimal graft retention and facial esthetic outcomes. PMID:26116934

  2. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

  3. Biotribological properties of UHMWPE grafted with AA under lubrication as artificial joint.

    PubMed

    Deng, Yaling; Xiong, Dangsheng; Wang, Kun

    2013-09-01

    Osteolysis caused by wear particles from polyethylene in the artificial hip joints is a serious issue. In order to endow the low friction and wear of the bearing surface of ultra-high molecular weight polyethylene (UHMWPE) artificial joint for a longer term, hydrophilic acrylic acid (AA) was grafted on UHMWPE powders with the method of ultraviolet irradiation and then the modified powders were hot pressed. The tribological properties of modified UHMWPE sliding against CoCrMo metallic plate on reciprocating tribometer under calf serum, saline and distilled water lubrication during a long-term friction were investigated. The measurement of Fourier-transform infrared spectroscopy indicates that AA is successfully grafted on the surface of UHMWPE powders by photo-induced graft polymerization. Contact angles of UHMWPE are decreased from 83° to 35° by grafting and the surface wettability is effectively improved. The tensile strength of modified sample decreases. The friction coefficient and wear rate of UHMWPE-g-PAA under calf serum, saline and distilled water lubrication are lower than that of untreated UHMWPE. With the increase of grafting ratio, the wear rate of UHMWPE-g-PAA decreases firstly and then increases. The modified UHMWPE with grafting ratio of 3.5 % has the lowest wear rate, which is just quarter of the untreated UHMWPE. The hydrated PAA polymer brushes enclosed in the UHMWPE bulk material provide continuous lubrication during long term sliding. PMID:23793532

  4. Hydrolyzed polyacrylamide grafted maize starch based microbeads: application in pH responsive drug delivery.

    PubMed

    Setty, C Mallikarjuna; Deshmukh, Anand S; Badiger, Aravind M

    2014-09-01

    The present study details the synthesis, characterization and pharmaceutical application of hydrolysed polyacrylamide grafted maize starch (HPam-g-MS) as promising polymeric material for the development of pH responsive microbeads. Different grades of graft copolymer were synthesized by changing the net microwave irradiation time, while keeping all other factors constant. Acute oral toxicity study performed in rodents ensured the bio-safety of graft copolymer for clinical application. Various batches of aceclofenac loaded microbeads were prepared by ionic gelation method using synthesized graft copolymers and evaluated for formulation parameters. FTIR spectroscopy confirmed the chemical compatibility between drug and graft copolymer. Results of in vitro release study (USP type-II) carried out in two different pH media (pH 1.2 acid buffer and pH 7.4 phosphate buffer) showed that release rate of drug from developed microbeads was a function of both: (a) surrounding pH and (b) the matrix composition. The drug release was relatively higher at alkaline pH as compared to acidic pH and this feature is desirable from viewpoint of site specific drug delivery. A direct correlation was observed between percentage grafting and microbeads performance and it presents a scope for further research on application and optimization of HPam-g-MS based microbeads as drug delivery carriers. PMID:24971555

  5. Encapsulation of clozapine in polymeric nanocapsules and its biological effects.

    PubMed

    Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof; Podgórna, Karolina; Błasiak, Ewa; Majeed, Nather; Ogren, Sven Ove Ögren; Nowak, Witold; Warszyński, Piotr; Dziedzicka-Wasylewska, Marta

    2016-04-01

    Clozapine is an effective atypical antipsychotic drug that unfortunately exhibits poor oral bioavailability. Moreover, the clinical use of the compound is limited because of its numerous unfavorable and unsafe side effects. Therefore, the aim of the present study was the development of a new nanocarrier for a more effective clozapine delivery. Here, clozapine was encapsulated into polymeric nanocapsules (NCs). Polyelectrolyte multilayer shells were constructed by the technique of sequential adsorption of polyelectrolytes (LbL) using biocompatible polyanion PGA (Poly-L-glutamic acid, sodium salt) and polycation PLL (poly-L-lysine) on clozapine-loaded nanoemulsion cores. Pegylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG (polyethylene glycol)). Clozapine was successfully loaded into the PLL-PGA nanocarriers (CLO-NCs) with an average size of 100 nm. In vitro analysis of the interactions of the CLO-NCs with the cells of the mononuclear phagocytic system (MPS) was conducted. Cell biocompatibility, phagocytosis potential, and cellular uptake were studied. Additionally, the biodistribution and behavioral effects of the encapsulated clozapine were also studied. The results indicate that surface modified (by PEG grafting) polymeric PLL-PGA CLO-NCs are very promising nanovehicles for improving clozapine delivery. PMID:26774571

  6. Biocompatible Polymeric Nanoparticles as Promising Candidates for Drug Delivery.

    PubMed

    Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof; Błasiak, Ewa; Dziedzicka-Wasylewska, Marta

    2015-06-16

    The use of polymeric nanoparticles (NPs) in pharmacology provides many benefits because this approach can increase the efficacy and selectivity of active compounds. However, development of new nanocarriers requires better understanding of the interactions between NPs and the immune system, allowing for the optimization of NP properties for effective drug delivery. Therefore, in the present study, we focused on the investigation of the interactions between biocompatible polymeric NPs and a murine macrophage cell line (RAW 264.7) and a human monocytic leukemia cell line (THP-1). NPs based on a liquid core with polyelectrolyte shells were prepared by sequential adsorption of polyelectrolytes (LbL) using AOT (docusate sodium salt) as the emulsifier and the biocompatible polyelectrolytes polyanion PGA (poly-l-glutamic acid sodium salt) and polycation PLL (poly l-lysine). The average size of the obtained NPs was 80 nm. Pegylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG poly(ethylene glycol)). The influence of the physicochemical properties of the NPs (charge, size, surface modification) on viability, phagocytosis potential, and endocytosis was studied. Internalization of NPs was determined by flow cytometry and confocal microscopy. Moreover, we evaluated whether addition of PEG chains downregulates particle uptake by phagocytic cells. The presented results confirm that the obtained PEG-grafted NPs are promising candidates for drug delivery. PMID:26013473

  7. Synthesis and characterization of macromolecular layers grafted to polymer surfaces

    NASA Astrophysics Data System (ADS)

    Burtovyy, Oleksandr

    The composition and behavior of surfaces and interfaces play a pivotal role in dictating the overall efficiency of the majority of polymeric materials and devices. Surface properties of the materials can be altered using surface modification techniques. It is necessary to highlight that successful methods of surface modification should affect only the upper layer of the polymer material without changing bulk properties. The processes must introduce new functionalities to the surface, optimize surface roughness, lubrication, hydrophobicity, hydrophilicity, adhesion, conductivity, and/or biocompatibility. Research presented in this dissertation is dedicated to the synthesis, characterization, and application of thin macromolecular layers anchored to polymer substrates. Specifically, attachment of functional polymers via a "grafting to" approach has been extensively studied using PET and nylon model substrates. First, poly(glycidyl methacrylate) was used to introduce permanent functionalities to the model substrates by anchoring it to model films. Then, three different functional polymers were grafted on top of the previous layer. As one part of this study, the temperature and time dependence of grafting functional layers were studied. The surface coverage by hydrophobic polymer was determined from experimental data and predicted by a model. In general, the model has a high degree of predictive capability. Next, surface modification of polymeric fibers and membranes is presented as an important application of the polymer thin layers targeted in the study. Specifically, the procedures developed for surface modification of model substrates was employed for modification of PET, nylon, and cotton fabrics as well as PET track-etched membranes. Since epoxy groups are highly reactive in various chemical reactions, the approach becomes virtually universal, allowing both various surfaces and end-functionalized macromolecules to be used in the grafted layer synthesis. PET

  8. Silicone hydrogels grafted with natural amino acids for ophthalmological application.

    PubMed

    Xu, Chen; He, Ruiyu; Xie, Binbin; Ismail, Muhammad; Yao, Chen; Luan, Jie; Li, Xinsong

    2016-09-01

    In this report, protein repelling silicone hydrogels with improved hydrophilicity were prepared by photo-polymerization of silicone-containing monomer and glycidyl methacrylate followed by grafting zwitterionic amino acids. The grafted silicone hydrogels possessed excellent hydrophilic surfaces due to the enrichment of amino acids, which was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle, and equilibrium water content measurements. Remarkable resistance to bovine serum albumin and lysozyme fouling was observed for the silicone hydrogels immobilized with neutrally charged amino acids because of the formation of zwitterionic surfaces with pairs of protonated secondary ammonium cations and deprotonated carboxyl anions. Meanwhile, the silicone hydrogels grafted with positively or negatively charged amino acids were able to repulse same charged protein with reduced deposition and attract oppositely charged protein with increased adsorption. Preliminary cytotoxicity test indicated that the zwitterionic silicone hydrogels were non-cytotoxic. Similarly, three types of natural amino acids, including serine, aspartic acid and histidine, modified silicone hydrogel contact lenses exhibited excellent hydrophilicity and non-damage to the rabbit's eyes, but only serine modified zwitterionic contact lens showed superior protein fouling resistance compared with the current commercial hydrogel contact lens, which may have great potential application in ophthalmology. PMID:27297564

  9. Bone Grafting the Cleft Maxilla

    MedlinePlus

    ... amount of bone from one place (usually the hip, head, ribs, or leg) and placing it in ... adjacent teeth into the bone graft; 2) prosthetic replacement (dental bridge); or 3) dental metallic bone implants. ...

  10. Preparation of metal adsorbent from poly(methyl acrylate)-grafted-cassava starch via gamma irradiation

    NASA Astrophysics Data System (ADS)

    Suwanmala, Phiriyatorn; Hemvichian, Kasinee; Hoshina, Hiroyuki; Srinuttrakul, Wannee; Seko, Noriaki

    2012-08-01

    Metal adsorbent containing hydroxamic acid groups was successfully synthesized by radiation-induced graft copolymerization of methyl acrylate (MA) onto cassava starch. The optimum conditions for grafting were studied in terms of % degree of grafting (Dg). Conversion of the ester groups present in poly(methyl acrylate)-grafted-cassava starch copolymer into hydroxamic acid was carried out by treatment with hydroxylamine (HA) in the presence of alkaline solution. The maximum percentage conversion of the ester groups of the grafted copolymer, % Dg=191 (7.63 mmol/g of MA), into the hydroxamic groups was 70% (5.35 mmol/g of MA) at the optimum condition. The adsorbent of 191%Dg had total adsorption capacities of 2.6, 1.46, 1.36, 1.15 and 1.6 mmol/g-adsorbent for Cd2+, Al3+, UO22+, V5+ and Pb2+, respectively, in the batch mode adsorption.

  11. Coating of plasma polymerized film

    NASA Technical Reports Server (NTRS)

    Morita, S.; Ishibashi, S.

    1980-01-01

    Plasma polymerized thin film coating and the use of other coatings is suggested for passivation film, thin film used for conducting light, and solid body lubrication film of dielectrics of ultra insulators for electrical conduction, electron accessories, etc. The special features of flow discharge development and the polymerized film growth mechanism are discussed.

  12. Modification of polysulfone membranes via surface-initiated atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Dong, Han-Bang; Xu, You-Yi; Yi, Zhuan; Shi, Jun-Li

    2009-08-01

    Hydrophilic poly((poly(ethylene glycol) methyl ether methacrylate) (P(PEGMA)) and poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surfaces via surface-initiated atom transfer radical polymerization (ATRP). Prior to ATRP, chloromethylation of PSF was performed beforehand and the obtained CMPSF was prepared into porous membranes by phase inversion process. It was demonstrated that the benzyl chloride groups on the CMPSF membrane surface afforded effective macroinitiators to graft the well-defined polymer brushes. 1H NMR was employed to confirm the structure of CMPSF. The grafting yield of P(PEGMA) and PGMA was determined by weight gain measurement. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the grafting of P(PEGMA) and PGMA chains. Water contact angle measurements indicated that the introduction of P(PEGMA) and PGMA graft chains promoted remarkably the surface hydrophilicity of PSF membranes. The effects of P(PEGMA) and PGMA immobilization on membrane morphology, permeability and fouling resistance were investigated. It was found that P(PEGMA) and PGMA grafts brought higher pure water flux, improved hydrophilic surface and better anti-protein absorption ability to PSF membranes after modification. And evidently, macromonomer P(PEGMA) brought much better properties to the PSF membranes than PGMA macromonomer.

  13. Experience of injected fat grafting.

    PubMed

    Matsudo, P K; Toledo, L S

    1988-02-01

    Eighteen months' experience with the injected fat grafting technique used in 208 patients to correct various problems such as buttocks (augmentation and reshaping), trochanteric depressions, breast augmentation, scar depressions, thighs and legs (calf and ankle augmentation), small wrinkles and depressions of the face (Romberg's disease), nasolabial fold, upper outer breast quadrant, liposuction sequela, fingers and hands is presented. This method shows major advantages with few complications. Some technical details and recommendations for successful fat grafting are also presented. PMID:3376783

  14. Interventions in Infrainguinal Bypass Grafts

    SciTech Connect

    Mueller-Huelsbeck, S. Order, B.-M.; Jahnke, T.

    2006-02-15

    The interventional radiologist plays an important role in the detection and prevention of infrainguinal bypass failure. Early detection and evaluation of flow-limiting lesions effectively preserve graft (venous bypass and polyester or expanded polytetrafluoroethylene bypass) patency by identifying stenoses before occlusion occurs. Delay in treatment of the at-risk graft may result in graft failure and a reduced chance of successful revascularization. For this reason, surveillance protocols form an important part of follow-up after infrainguinal bypass surgery. As well as having an understanding of the application of imaging techniques including ultrasound, MR angiography, CT angiography and digital subtraction angiography, the interventional radiologist should have detailed knowledge of the minimally invasive therapeutic options. Percutaneous transluminal angioplasty (PTA), or alternatively cutting balloon angioplasty, is the interventional treatment of choice in prevention of graft failure and occlusion. Further alternatives include metallic stent placement, fibrinolysis, and mechanical thrombectomy. Primary assisted patency rates following PTA can be up to 65% at 5 years. When the endovascular approach is unsuccessful, these therapeutic options are complemented by surgical procedures including vein patch revision, jump grafting, or placement of a new graft.

  15. Costal Grafting in Mandibular Reconstruction

    PubMed Central

    Bourlet, Jerôme; Château, Joseph; Jacquemart, Mathieu; Dufour, Clémence; Mojallal, Ali; Gleizal, Arnaud

    2015-01-01

    Background: Reconstruction of mandibular bone defect is a common indication in craniomaxillofacial surgery, and free fibular flap is the gold standard for this indication. However, there are alternatives; nonvascular bone grafting is one of them, and we present the costal grafting for mandibular reconstruction, a classic technique that is reliable, efficient, and produced less morbidity than the technique of using composite free flaps. Method: A 9-year retrospective review of 54 patients treated surgically for mandibular reconstruction was performed. The criterion mainly analyzed was graft survival. The surgical technique was described in detail. Results: A total of 54 patients with mandibular bone defect were identified. Five symphysis, 46 corpus, and 20 ramus defects were considered. These patients underwent reconstruction by costal grafting, and the engrafting was successful in 92.6% of cases. Dental rehabilitation with dental implants was realized in 70% of cases. Conclusions: The approach described in this article allowed the authors to obtain good results with costal grafting for mandibular reconstruction and dental rehabilitation. Costal grafting is a good alternative for fibula free flap in specific indications. Reconstruction of mandibular bone defect is a common indication in craniomaxillofacial surgery. Since the 1980s, the gold standard for these defects is the use of free fibular flap.1 In some cases, this technique is contradicted; the surgeon then has several possibilities for the use of free osteomyocutaneous flaps (iliac crest, scapula, and serrato-costal flaps).2–8 PMID:26893990

  16. Bilateral internal thoracic artery grafting

    PubMed Central

    2013-01-01

    The effectiveness of the left internal mammary artery graft to the anterior descending coronary artery as a surgical strategy has been shown to improve the survival rate and decrease the risk of adverse cardiac events in patients undergoing coronary bypass surgery. These clinical benefits appear to be related to the superior short and long-term patency rates of the internal thoracic artery graft. Although the advantages of using of both internal thoracic arteries (ITA) for bypass grafting have taken longer to prove, recent results from multiple data sets now support these findings. The major advantage of bilateral ITA grafting appears to be improved survival rate, while the disadvantages of complex ITA grafting include the increased complexity of operation, and an increased risk of wound complications. While these short-term disadvantages have been mitigated in contemporary surgical practice, they have not eliminated. Bilateral ITA grafting should be considered the procedure of choice for patients undergoing coronary bypass surgery that have a predicted survival rate of longer than ten years. PMID:23977627

  17. PLLA-grafted cellulose nanocrystals: Role of the CNC content and grafting on the PLA bionanocomposite film properties.

    PubMed

    Lizundia, Erlantz; Fortunati, Elena; Dominici, Franco; Vilas, José Luis; León, Luis Manuel; Armentano, Ilaria; Torre, Luigi; Kenny, Josè M

    2016-05-20

    Cellulose nanocrystals (CNC), extracted from microcrystalline cellulose by acid hydrolysis, were grafted by ring opening polymerization of L-Lactide initiated from the hydroxyl groups available at their surface and two different CNC:L-lactide ratios (20:80 and 5:95) were obtained. The resulting CNC-g-PLLA nanohybrids were incorporated in poly(lactic acid) (PLA) matrix by an optimized extrusion process at two different content (1 wt.% and 3 wt.%) and obtained bionanocomposite films were characterized by thermal, mechanical, optical and morphological properties. Thermal analysis showed CNC grafted with the higher ratio of lactide play a significant role as a nucleating agent. Moreover, they contribute to a significant increase in the crystallization rate of PLA, and the best efficiency was revealed with 3 wt.% of CNC-g-PLLA. This effect was confirmed by the increased in Young's modulus, suggesting the CNC graft ratio and content contribute significantly to the good dispersion in the matrix, positively affecting the final bionanocomposite properties. PMID:26917380

  18. Grafting of Chitosan and Chitosantrimethoxylsilylpropyl Methacrylate on Single Walled Carbon Nanotubes-Synthesis and Characterization

    PubMed Central

    Carson, Laura; Kelly-Brown, Cordella; Stewart, Melisa; Oki, Aderemi; Regisford, Gloria; Stone, Julia; Traisawatwong, Pasakorn; Durand-Rougely, Clarissa; Luo, Zhiping

    2011-01-01

    Acid functionalized single walled carbon nanotubes (CNTs) were grafted to chitosan by first reacting the oxidized CNTs with thionyl chloride to form acyl-chlorinated CNTs. This product was subsequently dispersed in chitosan and covalently grafted to form CNT-chitosan. CNT-chitosan was further grafted onto 3-trimethoxysilylpropyl methacrylate by free radical polymerization conditions, to yield CNT-g-chitosan-g-3-trimethoxysilylpropyl methacrylate (TMSPM), hereafter referred to as CNT-chitosan-3-TMSPM. These composites were characterized by Fourier Transform Infrared Resonance Spectroscopy (FTIR), carbon-13 nuclear magnetic resonance (13C NMR), Thermogravimetric Analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The composite showed improved thermal stability and could be of great potential use in bone tissue engineering. PMID:21765959

  19. Polysulfone functionalized with phosphonated poly(pentafluorostyrene) grafts for potential fuel cell applications.

    PubMed

    Dimitrov, Ivaylo; Takamuku, Shogo; Jankova, Katja; Jannasch, Patric; Hvilsted, Søren

    2012-08-28

    A multi-step synthetic strategy to polysulfone (PSU) grafted with phosphonated poly(pentafluorostyrene) (PFS) is developed. It involves controlled radical polymerization resulting in alkyne-end functional PFS. The next step is the modification of PSU with a number of azide side groups. The grafting of PFS onto PSU backbone is performed via the "click"-chemistry approach. In a final step, the PFS-grafts are subjected to the post phosphonation. The copolymers are evaluated as membranes for potential fuel cell applications through thermal analyses, water uptake, and conductivity measurements. The proposed synthetic route opens the possibility to tune copolymers' hydrophilic-hydrophobic balance to obtain membranes with an optimal balance between proton conductivity and mechanical properties. PMID:22623205

  20. Grafted synthetic sorbents for enhanced removal of toxic chemical agents from plasma.

    PubMed

    McPhillips, D M; Armer, T A; Owen, D R

    1983-11-01

    A series of porous polymeric sorbents and activated carbon were used to remove diisopropyl methylphosphonate (DIMP) from human plasma and normal saline. The sorptive capacities of the commercially available sorbents Amberlite XAD-4, XAD-2, XN1010, and XE348, and Calgon 400 were determined. Butyl- and palmityl-grafted XAD-4 were prepared with graft efficiencies of 32 and 6%, respectively, and tested for sorptive capacities. DIMP removal efficiencies were compared to dialysis with a 1.8 m2 Cordis-Dow hollow fiber artificial kidneY (HFAK). Butyl-grafted XAD-4 and active carbon outperformed the other sorbents in removing DIMP from both saline and plasma. An order of magnitude reduction in removal ability was noted for all the adsorbents when the mobile media was plasma. Pronounced plasma precipitation was elicited by activated carbon, an effect not observed with any of the polymeric resins tested. The removal efficiencies on a 18.0 g basis of XAD-4, butyl-grafted XAD-4, and active carbon were comparable to that of the HFAK used in this study. These sorbents, however, possess a macroscopic surface area of approximately 0.1 m2, an order of magnitude lower than that of the HFAK. This reduction in contact area is believed to reduce substantially the possibility of undesirable molecular and cellular effects. PMID:6654935

  1. Polyaspartamide-Polylactide Graft Copolymers with Tunable Properties for the Realization of Fluorescent Nanoparticles for Imaging.

    PubMed

    Craparo, Emanuela Fabiola; Porsio, Barbara; Mauro, Nicolò; Giammona, Gaetano; Cavallaro, Gennara

    2015-08-01

    Here, the synthesis and the characterization of novel amphiphilic graft copolymers with tunable properties, useful in obtaining polymeric fluorescent nanoparticles for application in imaging, are described. These copolymers are obtained by chemical conjugation of rhodamine B (RhB) moieties, polylactic acid (PLA), and O-(2-aminoethyl)-O'-methyl poly(ethylene glycol) (PEG) on α,β-poly(N-2-hydroxyethyl)-D,L-aspartamide (PHEA). In particular, PHEA is first functionalized with RhB to obtain PHEA-RhB with a derivatization degree in RhB (DDRhB ) equal to 0.55 mol%. By varying the reaction conditions, different amounts of PLA are grafted on PHEA-RhB to obtain PHEA-RhB-PLA with DDPLA equal to 1.9, 4.0, and 6.2 mol%. Then, PEG chains are grafted on PHEA-RhB-PLA derivatives to obtain PHEA-RhB-PLA-PEG graft copolymers. The preparation of polymeric fluorescent nanoparticles with tunable properties and spherical shape is described by using PHEA-RhB-PLA-PEG with DD in PLA and PEG equal to 4.0 and 4.9 mol%, by following easily scaling up processes, such as emulsion-solvent evaporation and high pressure homogenization (HPH)-solvent evaporation techniques. PMID:26010226

  2. Starch graft poly(methyl acrylate) loose-fill foam: preparation, properties and degradation.

    PubMed

    Chen, L; Gordon, S H; Imam, S H

    2004-01-01

    Starch graft poly(methyl acrylate) (S-g-PMA) was prepared by ceric ion initiation of methyl acrylate in an aqueous corn starch slurry (prime starch) which maximized the accessibility of the starch for graft polymerization. A new ceric ion reaction sequence was established as starch-initiator-methyl acrylate followed by addition of a small amount of ceric ion solution when the graft polymerization was almost complete to quench the reaction. As a result of this improved procedure, no unreacted methyl acrylate monomer remained, and thus, essentially no ungrafted poly(methyl acrylate) homopolymer was formed in the final grafted product. Quantities of the high purity S-g-PMA so prepared in pilot scale were converted to resin pellets and loose-fill foam by single screw and twin screw extrusion. The use of prime starch significantly improved the physical properties of the final loose-fill foam, in comparison to foam produced from regular dry corn starch. The S-g-PMA loose-fill foam had compressive strength and resiliency comparable to expanded polystyrene but higher bulk density. The S-g-PMA loose-fill foam also had better moisture and water resistance than other competitive starch-based materials. Studies indicated that the starch portion in S-g-PMA loose-fill foam biodegraded rapidly, whereas poly(methyl acrylate) remained relatively stable under natural environmental conditions. PMID:14715032

  3. Synthesis of dendrigraft poly(ϵ-caprolactone)s using side hydroxyl groups for the grafting of branch chains.

    PubMed

    Cheng, Juan; Ling, Xiujun; Zhong, Zhenlin; Zhuo, Renxi

    2011-11-15

    Dendrigraft poly(ϵ-caprolactone)s with high molecular weight and narrow polydispersity are synthesized via a convenient generation-growth approach. Copolymerization of ϵ-caprolactone (CL) and 4-(2-benzoxyethoxy)-ϵ-caprolactone (BECL) with stannous octanoate as a catalyst affords a functionalized poly(ϵ-caprolactone) (PCL) with benzyl-protected hydroxyl side groups. After removal of benzyl groups by palladium-catalyzed hydrogenolysis, the graft copolymerization of CL and BECL onto the hydroxyl-bearing linear polyester (zero-generation) affords the first-generation graft polyester. Further deprotection and graft polymerization cycles led to dendrigraft polyesters. Molecular weights are multiplied in each graft copolymerization. The second-generation dendrigraft poly(ϵ-caprolactone) has an M(w) of 236 000 g·mol(-1) and M(w) /M(n) of 1.53. PMID:21928304

  4. Primary Graft Dysfunction

    PubMed Central

    Christie, Jason D

    2014-01-01

    Primary graft dysfunction (PGD) is a syndrome encompassing a spectrum of mild to severe lung injury that occurs within the first 72 hours after lung transplantation. PGD is characterized by pulmonary edema with diffuse alveolar damage that manifests clinically as progressive hypoxemia with radiographic pulmonary infiltrates. In recent years, new knowledge has been generated on risks and mechanisms of PGD. Following ischemia and reperfusion, inflammatory and immunological injury-repair responses appear to be key controlling mechanisms. In addition, PGD has significant impact on short- and long-term outcomes; therefore, the choice of donor organ is impacted by this potential adverse consequence. Improved methods of reducing PGD risk and efforts to safely expand the pool are being developed. Ex-vivo lung perfusion is a strategy which may improve risk assessment and become a promising platform to implement treatment interventions to prevent PGD. This review will detail recent updates in the epidemiology, pathophysiology, molecular and genetic biomarkers and state-of-the-art technical developments affecting PGD. (158 words) PMID:23821506

  5. Polymerization topochemistry of cellulose nanocrystals: a function of surface dehydration control.

    PubMed

    Tian, Chen; Fu, Shiyu; Habibi, Youssef; Lucia, Lucian A

    2014-12-01

    The activation (dehydration) of cellulose nanocrystals (CNCs) toward surface "brush" polymerization is accomplished either by freeze drying or solvent exchange. However, the question of which one of these protocols to choose over the other is generally open-ended. The current study attempts to shed light on this question by installing a standard polymer, polycaprolactone (PCL), onto the surface of both freeze-dried and solvent-exchanged CNCs by ring-opening polymerization (ROP) and examining the differences in polymerization and final product properties. The work is the first to demonstrate that the efficiency of surface polymerization and final product properties are in fact influenced by the protocols. The differences between the two sample PCL-grafted CNCs were investigated by X-ray photoelectron spectroscopy (XPS), elemental analysis, gel permeation chromatography (GPC), and contact-angle measurements. The freeze-dried samples had a significantly reduced PCL surface density. The crystallinity of the solvent-exchanged PCL-grafted CNCs (SECNC-g-PCL), however, was lower than that of either pure CNCs or freeze-dried PCL-grafted CNCs (FDCNC-g-PCL). It was determined that solvent exchange sufficiently modified the CNC surface to provide enhanced reactivity, an effect that was not as apparent for FDCNC-g-PCL. The solvent-exchanged CNCs tended to have more porous, nanotextured surfaces that were tended to be more responsive toward brush polymerization. In addition to the physical dissimilarities in surface morphology and surface accessibility contributing to topochemical differences between the two species, it was also found that the dispersibility, aggregation, and thermal stability were different. PMID:25387043

  6. A spun elastomeric graft for dialysis access.

    PubMed

    Drasler, W J; Wilson, G J; Stenoien, M D; Jenson, M L; George, S A; Dutcher, R G; Possis, Z C

    1993-01-01

    A new composite vascular graft was developed using electrostatic spinning technology. The graft is primarily microfibrous polydimethylsiloxane spun onto a mandrel; a small diameter polyester yarn provides additional strength while minimizing wall thickness, and a helical bead provides crush and kink resistance. Eighteen grafts were implanted in a mongrel canine arteriovenous shunt model for 12 months. The grafts were implanted in femoral artery to femoral vein loops and were cannulated using three pairs of 16 gauge dialysis needles per week. Grafts were evaluated during each puncture session, and also followed using angiography. Histologic study of explanted grafts, regional lymph nodes, and lungs was performed. The grafts provided excellent handling and puncture characteristics, with no bleeding through the graft wall at puncture sites. Cumulative patency of these punctured grafts was 88% at 6 months and 80% at 1 year. Histologic study showed external fibroconnective tissue encapsulation of the grafts, with tissue growth through the interstices of the graft consisting of a microvascular network surrounded predominantly by histiocytes, many multinucleated foreign body giant cells, with some fibroblasts and collagen formation also present. Little luminal thrombus was seen at puncture sites in the patent grafts, and there was no evidence of pulmonary thromboemboli. This new elastomeric graft shows excellent promise for dialysis access; similar grafts under development may also find application for small diameter peripheral vascular reconstruction. PMID:8324257

  7. Preparation of polystyrene brush film by radical chain-transfer polymerization and micromechanical properties

    NASA Astrophysics Data System (ADS)

    Zhao, Jing; Chen, Miao; An, Yanqing; Liu, Jianxi; Yan, Fengyuan

    2008-12-01

    A radical chain-transfer polymerization technique has been applied to graft-polymerize brushes of polystyrene (PSt) on single-crystal silicon substrates. 3-Mercapto-propyltrimethoxysilane (MPTMS), as a chain-transfer agent for grafting, was immobilized on the silicon surface by a self-assembling process. The structure and morphology of the graft-functionalized silicon surfaces were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, Fourier transformation infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The nanotribological and micromechanical properties of the as-prepared polymer brush films were investigated by frictional force microscopy (FFM), force-volume analysis and scratch test. The results indicate that the friction properties of the grafted polymer films can be improved significantly by the treatment of toluene, and the chemically bonded polystyrene film exhibits superior scratch resistance behavior compared with the spin-coated polystyrene film. The resultant polystyrene brush film is expected to develop as a potential lubrication coating for microelectromechanical systems (MEMS).

  8. Brush/gold nanoparticle hybrids: effect of grafting density on the particle uptake and distribution within weak polyelectrolyte brushes.

    PubMed

    Christau, Stephanie; Möller, Tim; Yenice, Zuleyha; Genzer, Jan; von Klitzing, Regine

    2014-11-01

    The effect of the brush grafting density on the loading of 13 nm gold nanoparticles (AuNPs) into stimuli-responsive poly(N,N-(dimethylamino ethyl) methacrylate) (PDMAEMA) brushes anchored to flat impenetrable substrates is reported. Atom-transfer radical polymerization (ATRP) is used to grow polymer brushes via a "grafting from" approach from a 2-bromo-2-methyl-N-(3-(triethoxysilyl) propyl) propanamide (BTPAm)-covered silicon substrate. The grafting density is varied by using mixtures of initiator and a "dummy" molecule that is not able to initiate polymerization. A systematic study is carried out by varying the brush grafting density while keeping all of the other parameters constant. X-ray reflectivity is a suitable tool for investigating the spatial structure of the hybrid, and it is combined with scanning electron microscopy and UV/vis spectroscopy to study the particle loading and interpenetration of the particles within the polymer brush matrix. The particle uptake increases with decreasing grafting density and is highest for an intermediate grafting density because more space between the polymer chains is available. For very low grafting densities of PDMAEMA brushes, the particle uptake decreases because of a lack of the polymer matrix for the attachment of particles. The structure of the surface-grafted polymer chains changes after particle attachment. More water is incorporated into the brush matrix after particle immobilization, which leads to a swelling of the polymer chains in the hybrid material. Water can be removed from the brush by decreasing the relative humidity, which leads to brush shrinking and forces the AuNPs to get closer to each other. PMID:25275215

  9. Grafting titanium nitride surfaces with sodium styrene sulfonate thin films.

    PubMed

    Zorn, Gilad; Migonney, Véronique; Castner, David G

    2014-09-01

    The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm(2). PMID:25280842

  10. Grafting titanium nitride surfaces with sodium styrene sulfonate thin films

    PubMed Central

    Zorn, Gilad; Migonney, Véronique; Castner, David G.

    2014-01-01

    The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm2. PMID:25280842

  11. Stability of Grafted Polymer Nanoscale Films toward Gamma Irradiation.

    PubMed

    Borodinov, Nikolay; Giammarco, James; Patel, Neil; Agarwal, Anuradha; O'Donnell, Katie R; Kucera, Courtney J; Jacobsohn, Luiz G; Luzinov, Igor

    2015-09-01

    The present article focuses on the influence of gamma irradiation on nanoscale polymer grafted films and explores avenues for improvements in their stability toward the ionizing radiation. In terms of applications, we concentrate on enrichment polymer layers (EPLs), which are polymer thin films employed in sensor devices for the detection of chemical and biological substances. Specifically, we have studied the influence of gamma irradiation on nanoscale poly(glycidyl methacrylate) (PGMA) grafted EPL films. First, it was determined that a significant level of cross-linking was caused by irradiation in pure PGMA films. The cross-linking is accompanied by the formation of conjugated ester, carbon double bonds, hydroxyl groups, ketone carbonyls, and the elimination of epoxy groups as determined by FTIR. Polystyrene, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, dimethylphenylsilanol, BaF2, and gold nanoparticles were incorporated into the films and were found to mitigate different aspects of the radiation damage. PMID:26259102

  12. Should computed tomography angiography supersede invasive coronary angiography for the evaluation of graft patency following coronary artery bypass graft surgery?

    PubMed

    Gabriel, Joseph; Klimach, Stefan; Lang, Peter; Hildick-Smith, David

    2015-08-01

    Invasive coronary angiography (ICA) has long been the established gold standard in assessing graft patency following coronary artery bypass graft (CABG). Over the past decade or so however, improvements in computed tomography angiography (CTA) technology have allowed its emergence as a useful clinical tool in graft assessment. The recent introduction of 64-slice and now 128-slice scanners into widespread distribution, and the development of 320-detector row technology allowing volumetric imaging of the entire heart at single points in time within one cardiac cycle, has increased the potential of CTA to supersede ICA in this capacity. This study sought to examine the evidence surrounding this potential. A best evidence topic was constructed according to a structured protocol. The enquiry: In [patients who have undergone coronary artery bypass graft surgery] is [computed tomography angiography or invasive coronary angiography] superior in terms of [graft patency assessment, stenosis detection, radiation exposure and complication rate]? Four hundred and twenty-four articles were identified from the search strategy. Four additional articles were identified from references of key articles. Seventeen articles selected as best evidence were tabulated. The reliability of CTA as a tool in the detection of graft patency and stenosis has continued to improve with each successive generation of multislice technology. The latest 64- and 128-slice CTA techniques are able to detect graft patency and stenosis with very high sensitivities and specificities comparable with ICA, while remaining non-invasive procedures associated with fewer complications (ICA carries a 0.08% risk of myocardial infarction and 0.7% risk of minor complications in clinically stable patients). Present limitations of the technology include the accurate visualization of distal anastomoses and clip artefacts. In addition, the capacity of diagnostic ICA to be combined simultaneously with percutaneous coronary

  13. Melting line of polymeric nitrogen

    NASA Astrophysics Data System (ADS)

    Yakub, L. N.

    2013-05-01

    We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

  14. Developments at the graft interface in homo- and hetero-grafts

    PubMed Central

    Clemente Moreno, Maria José; Hevin, Cyril; Ollat, Nathalie; Cookson, Sarah Jane

    2014-01-01

    Gene expression changes induced during graft union formation (the first month after grafting) in grapevine have been studied using whole genome microarrays. The genes differentially expressed between the rootstock and graft interface tissues of homo-grafts (Cabernet Sauvignon (CS) grafted onto CS) were compared at 3 and 28 days after grafting (dag). Graft union formation was associated with the upregulation of genes involved in secondary metabolism, cell wall, wound responses and hormone signaling. These gene expression differences were associated with the accumulation of lignin, cellulose and callose in the callus cells. Superimposed upon this, hetero-grafting between two different grapevine genotypes resulted in the further upregulation of stress and/or defense responses at the graft interface. Here we discuss the limitations of the techniques used to study the developments at the graft interface to date and future research directions to understand graft union formation in plants. PMID:24770337

  15. High temperature structural, polymeric foams from high internal emulsion polymerization

    SciTech Connect

    Hoisington, M.A.; Duke, J.R.; Apen, P.G.

    1996-02-01

    In 1982, a high internal phase emulsion (HIPE) polymerization process to manufacture microcellular, polymeric foam systems was patented by Unilever. This patent discloses a polymerization process that occurs in a water-in-oil emulsion in which the water represents at least 76% of the emulsion by volume. The oil phase consists of vinyl monomers such as styrene and acrylates that are crosslinked by divinyl monomers during polymerization. After polymerization and drying to remove the water phase, the result is a crosslinked polymer foam with an open cell microstructure that is homogeneous throughout in terms of morphology, density, and mechanical properties. Since 1982, numerous patents have examined various HIPE polymerized foam processing techniques and applications that include absorbents for body fluids, cleaning materials, and ion exchange systems. All the published HIPE polymerized foams have concentrated on materials for low temperature applications. Copolymerization of styrene with maleic anhydride and N-substituted maleimides to produce heat resistant thermoplastics has been studied extensively. These investigations have shown that styrene will free radically copolymerize with N-substituted maleimides to create an alternating thermoplastic copolymer with a Tg of approximately 200{degrees}C. However, there are many difficulties in attempting the maleimide styrene copolymerization in a HIPE such as lower polymerization temperatures, maleimide solubility difficulties in both styrene and water, and difficulty obtaining a stable HIPE with a styrene/maleimide oil phase. This work describes the preparation of copolymer foams from N-ethylmaleimide and Bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane with styrene based monomers and crosslinking agents.

  16. Electrochemical deposition and surface-initiated RAFT polymerization: protein and cell-resistant PPEGMEMA polymer brushes.

    PubMed

    Tria, Maria Celeste R; Grande, Carlos David T; Ponnapati, Ramakrishna R; Advincula, Rigoberto C

    2010-12-13

    This paper introduces a novel and versatile method of grafting protein and cell-resistant poly(poly ethylene glycol methyl ether methacrylate) (PPEGMEMA) brushes on conducting Au surface. The process started with the electrochemical deposition and full characterization of an electro-active chain transfer agent (CTA) on the Au surface. The electrochemical behavior of the CTA was investigated by cyclic voltammetry (CV) while the deposition and stability of the CTA on the surface were confirmed by ellipsometry, contact angle, and X-ray photoelectron spectroscopy (XPS). The capability of the electrodeposited CTA to mediate surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization on both the polymethyl methacrylate (PMMA; model polymer) and PPEGMEMA brushes was demonstrated by the increase in thicknesses of the films after polymerization. Contact angles also decreased with the incorporation of the more hydrophilic brushes. Significant changes in the morphologies of the films before and after polymerization were also observed with atomic force microscopy (AFM) analyses. Furthermore, XPS results showed an increase in the O 1s peak intensity relative to C 1s after polymerizations, which confirmed the grafting of polyethyleneglycol (PEG) bearing brushes. The ability of the PPEGMEMA-modified Au surface to resist nonspecific adhesion of proteins and cells was monitored and confirmed by XPS, ellipsometry, contact angle, AFM, and fluorescence imaging. The new method presented has potential application as robust protein and cell-resistant coatings for electrically conducting electrodes and biomedical devices. PMID:21028799

  17. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  18. Saphenous vein forearm grafts and gortex thigh grafts as alternative forms of vascular access.

    PubMed

    Bhandari, S; Wilkinson, A; Sellars, L

    1995-11-01

    To compare the survival and complication rates of saphenous vein forearm grafts and gortex thigh grafts. Retrospective study over a twelve-year period with review of case-notes. Saphenous vein forearm grafts were constructed in 17 males and 12 females, mean age 61 years and gortex thigh grafts in 24 males and 22 females (49 grafts), mean age 49 years. Grafts were the primary form of access in 9 patients in each group. Follow-up was 45.6 and 135.2 patient years on dialysis for forearm grafts and thigh grafts respectively. One-year total survival was 89.4% (89.4% at 2 years and 71.5% at 3 years) and 84.9% (82.3% at 2 years and 70.4% at 3 years) for saphenous vein forearm grafts and gortex thigh grafts respectively. The overall complication rates were 0.22 and 0.61 per patient year on dialysis for saphenous vein forearm grafts and gortex thigh grafts respectively. Thrombosis occurred in 10% and 52%, infection in 0% and 35% and no complications in 62% and 24% of saphenous vein forearm grafts and gortex thigh grafts respectively. Both saphenous vein forearm grafts and gortex thigh grafts can provide satisfactory vascular access. The survival is similar at one year but gortex thigh grafts have a higher complication rate. PMID:8605714

  19. Graft copolymers of ethyl methacrylate on waxy maize starch derivatives as novel excipients for matrix tablets: physicochemical and technological characterisation.

    PubMed

    Marinich, J A; Ferrero, C; Jiménez-Castellanos, M R

    2009-05-01

    Nowadays, graft copolymers are being used as an interesting option when developing a direct compression excipient for controlled release matrix tablets. New graft copolymers of ethyl methacrylate (EMA) on waxy maize starch (MS) and hydroxypropylstarch (MHS) were synthesised by free radical polymerization and alternatively dried in a vacuum oven (OD) or freeze-dried (FD). This paper evaluates the performance of these new macromolecules and discusses the effect of the carbohydrate nature and drying process on their physicochemical and technological properties. Grafting of EMA on the carbohydrate backbone was confirmed by IR and NMR spectroscopy, and the grafting yields revealed that graft copolymers present mainly a hydrophobic character. The graft copolymerization also leads to more amorphous materials with larger particle size and lower apparent density and water content than carbohydrates (MS, MHS). All the products show a lack of flow, except MHSEMA derivatives. MSEMA copolymers underwent much plastic flow and less elastic recovery than MHSEMA copolymers. Concerning the effect of drying method, FD derivatives were characterised by higher plastic deformation and less elasticity than OD derivatives. Tablets obtained from graft copolymers showed higher crushing strength and disintegration time than tablets obtained from raw starches. This behaviour suggests that these copolymers could be used as excipients in matrix tablets obtained by direct compression and with a potential use in controlled release. PMID:19146956

  20. Synthesis and characterization of a novel graft copolymer of partially carboxymethylated guar gum and N-vinylformamide.

    PubMed

    Mishra, Madan Mohan; Mishra, Dinesh Kumar; Mishra, Pushyamitra; Behari, Kunj

    2015-01-22

    Graft copolymer of partially carboxymethylated guar gum (CMGOH) and N-vinylformamide (NVF) was synthesized by free radical polymerization using 2,2-Azobis [2-(2-imadazolin-2-yl) propane] dihydrochloride (AIPH) as initiator. The effect of various reaction parameters such as concentration of NVF, CMGOH, sulphuric acid and AIPH, as well as reaction time and temperature were investigated, and the grafting conditions were optimized. Percent total conversion, % grafting, grafting efficiency (%) and percent add on under different conditions were evaluated and compared. The reaction mechanism for graft copolymerization discussed. Studies on swelling, metal ion uptake and flocculation properties were carried out in aqueous medium and the results obtained are presented and discussed. Both CMGOH and its corresponding graft copolymer samples were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Looking at the reasonable results obtained, the synthesized graft copolymers CMGOH-g-NVF, may be exploited as potential candidates for some industrial important applications as flocculent superabsorbent, and other similar applications. PMID:25439961